RESOURCES

Abstract
We here demonstrate the preparation of composite polymer electrolytes (CPEs) for Li-ion batteries, applicable for 3D printing process via fused deposition modeling. The prepared composites consist of modified poly(ethylene glycol) (PEG), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and SiO2-based nanofillers. PEG was successfully end group modified yielding telechelic PEG containing either ureidopyrimidone (UPy) or barbiturate moieties, capable to form supramolecular networks via hydrogen bonds, thus introducing self-healing to the electrolyte system. Silica nanoparticles (NPs) were used as a filler for further adjustment of mechanical properties of the electrolyte to enable 3D-printability. The surface functionalization of the NPs with either ionic liquid (IL) or hydrophobic alkyl chains is expected to lead to an improved dispersion of the NPs within the polymer matrix. Composites with different content of NPs (5%, 10%, 15%) and LiTFSI salt (EO/Li+ = 5, 10, 20) were analyzed via rheology for a better understanding of 3D printability, and via Broadband Dielectric Spectroscopy (BDS) for checking their ionic conductivity. The composite electrolyte PEG 1500 UPy2/LiTFSI (EO:Li 5:1) mixed with 15% NP-IL was successfully 3D printed, revealing its suitability for application as printable composite electrolytes.

Abstract
Additive manufacturing has a wide range of applications and has opened up new methods of drug formulation, in turn achieving attention in medicine. We prepared styrene–isobutylene–styrene triblock copolymers (SIBS; Mn = 10 kDa–25 kDa, PDI 1,3–1,6) as a drug carrier for triamcinolone acetonide (TA), further processed by fused deposition modeling to create a solid drug release system displaying improved bioavailability and applicability. Living carbocationic polymerization was used to exert control over block length and polymeric architecture. Thermorheological properties of the SIBS polymer (22.3 kDa, 38 wt % S) were adjusted to the printability of SIBS/TA mixtures (1–5% of TA), generating an effective release system effective for more than 60 days. Continuous drug release and morphological investigations were conducted to probe the influence of the 3D printing process on the drug release, enabling 3D printing as a formulation method for a slow-release system of Triamcinolone.

Abstract
The polymer/solvent system poly(l-lactic acid)/ethyl butylacetylaminopropionate (PLLA/IR3535) is regarded as an insect-repellent-delivery system, serving, e.g., for fighting mosquito-borne tropical diseases. In such systems the solid polymer hosts the liquid repellent, with the latter slowly released to the environment, expelling mosquitoes. As a new approach, exceeding prior work about application of different technologies to obtain such devices, in this work, samples of the polymer/repellent system PLLA/IR3535 were prepared by 3D-printing. The experiments showed that it is possible to print 3D-parts containing up to 25 m% repellent, with an only minor loss of repellent during the printing process. For samples containing low amount of repellent, crystallization of PLLA was suppressed due to the rather fast cooling step and the low bed temperature of around 25 °C, being lower than the glass transition temperature of the homogeneous polymer/repellent strands. At higher repellent concentration, due to the lowering of the glass transition temperature to near or even below ambient temperature, the crystallinity slowly increased during storage after printing. For all samples, regardless of the initial repellent concentration, the repellent-release rate increases with temperature, and at ambient temperature the release-time constant is in the order of 10 days. The study successfully proved the applicability of the technology of extrusion-based 3D-printing for the preparation of polymer parts with a specific shape/design containing mosquito-repellent at a concentration which raises the expectation to be used as a repellent delivery-device.

Abstract
Abstract Here, the 3D-printing of supramolecular polymer electrolytes is reported, able to be manufactured via 3D-printing processes, additionally dynamically compensating for volume changes. A careful mechanical design, in addition to rheological effects observed for different additives to the electrolyte, is investigated and adjusted, in order to achieve printability via an extrusion process to generate a conductive electrode material. Qudruple-hydrogen bonds (UPy) act as supramolecular entities for the desired dynamic properties to adjust printability, in addition to added LiTFSi-salts to achieve ionic conductivities of ≈10–4 S cm–1 at T = 80 °C. Three different telechelic UPy-PEO/PPO-UPy-polymers with molecular weights ranging from Mn = 600–1500 g mol−1 were investigated in view of their 3D-printability by FDM-processes. It is found that there are three effects counterbalancing the rheological properties of the polymers: besides temperatures, which can be used as a known tool to adjust melt-rheology, also the addition of lithium-salts in junction with the polymers crystallinity exerts a major toolbox to 3D-print these electrolytes. Using specific compositions with Li/EO-ratios from 20:1, 10:1, and 5:1, the rheological profile can be adjusted to reach the required printability window. AT-IR-investigations clearly indicate a weakening of the UPy-bonds by the added Li+ ions, in addition to a reduction of the crystallinity of the PEO-units, further changing the rheological profile. The so generated electrolytes are printable systems for novel electrolytes.

Abstract
Abstract 3D printing of multicomponent materials as an advantageous method over traditional mold casting methods is demonstrated, developing small core–shell capsule composites fabricated by a two-step 3D printing process. Using a two-print-head system (fused deposition modeling extruder and a liquid inkjet print head), micro-sized capsules are manufactured in sizes ranging from 100 to 800 µm. The thermoplastic polymer poly(ε-caprolactone) (PCL) is chosen as matrix/shell material due to its optimal interaction with the embedded hydrophobic liquids. First, the core–shell capsules are printed with model liquids and pure PCL to optimize the printing parameters and to ensure fully enclosed capsules inside the polymer. As a proof of concept, novel “click” reaction systems, used in self-healing and stress-detection applications, are manufactured in which PCL composites with nano- and micro-fillers are combined with reactive, encapsulated liquids. The so generated 3D printed core–shell capsule composite can be used for post-printing reactions and damage sensing when combined with a fluorogenic dye.

Abstract
Abstract The preparation and characterization of mechanoresponsive, 3D-printed composites are reported using a dual-printing setup for both, liquid dispensing and fused-deposition-modeling. The here reported stress-sensing materials are based on high- and low molecular weight mechanophores, including poly(ε-caprolactone)-, polyurethane-, and alkyl(C11)-based latent copper(I)bis(N-heterocyclic carbenes), which can be activated by compression to trigger a fluorogenic, copper(I)-catalyzed azide/alkyne “click”-reaction of an azide-functionalized fluorescent dye inside a bulk polymeric material. Focus is placed on the printability and postprinting activity of the latent mechanophores and the fluorogenic “click”-components. The multicomponent specimen containing both, azide and alkyne, are manufactured via a 3D-printer to place the components separately inside the specimen into void spaces generated during the FDM-process, which subsequently are filled with liquids using a separate liquid dispenser, located within the same 3D-printing system. The low-molecular weight mechanophores bearing the alkyl-C11 chains display the best printability, yielding a mechanochemical response after the 3D-printing process.

Abstract
We present a comprehensive investigation of mechanical properties of supramolecular polymer networks with rationally developed multistrength hydrogen-bonding interactions. Self-healing poly(dimethylsiloxane) (PDMS)-based elastomers with varying elasticity, fracture toughness, and the ability to dissipate strain energy through the reversible breakage and re-formation of the supramolecular interactions were obtained. By changing the ratio between isophorone diisocyanate (IU), 4,4′-methylenebis(cyclohexyl isocyanate) (MCU), and 4,4′-methylenebis(phenyl isocyanate) (MPU) and by varying the molecular weight of the PDMS precursor, we obtained a library of poly(urea)s to study the interplay of mechanical performance and self-healability. The Young’s moduli of the presented materials ranged between 0.4 and 13 MPa and increased with decreasing molecular weight of the PDMS precursor and increasing content of MCU or MPU units related to the formation of stronger hydrogen-bonding interactions. By exchanging MPU against MCU units, we achieved an optimum balance between mechanical properties and self-healing performance, and by the additional reduction of the molecular weight of the precursor polymer, a minimum recovery of 80% in stress within 12 h at room temperature was observed. Selected poly(urea)s could be processed via 3D printing by the conventional extrusion method, obtaining dimensionally stable and freestanding objects.
We present a comprehensive investigation of mechanical properties of supramolecular polymer networks with rationally developed multistrength hydrogen-bonding interactions. Self-healing poly(dimethylsiloxane) (PDMS)-based elastomers with varying elasticity, fracture toughness, and the ability to dissipate strain energy through the reversible breakage and re-formation of the supramolecular interactions were obtained. By changing the ratio between isophorone diisocyanate (IU), 4,4′-methylenebis(cyclohexyl isocyanate) (MCU), and 4,4′-methylenebis(phenyl isocyanate) (MPU) and by varying the molecular weight of the PDMS precursor, we obtained a library of poly(urea)s to study the interplay of mechanical performance and self-healability. The Young’s moduli of the presented materials ranged between 0.4 and 13 MPa and increased with decreasing molecular weight of the PDMS precursor and increasing content of MCU or MPU units related to the formation of stronger hydrogen-bonding interactions. By exchanging MPU against MCU units, we achieved an optimum balance between mechanical properties and self-healing performance, and by the additional reduction of the molecular weight of the precursor polymer, a minimum recovery of 80% in stress within 12 h at room temperature was observed. Selected poly(urea)s could be processed via 3D printing by the conventional extrusion method, obtaining dimensionally stable and freestanding objects.

Abstract
Abstract 3D printing of linear and three-arm star supramolecular polymers with attached hydrogen bonds and their nanocomposites is reported. The concept is based on hydrogen-bonded supramolecular polymers, known to form nano-sized micellar clusters. Printability is based on reversible thermal- and shear-induced dissociation of a supramolecular polymer network, which generates stable and self-supported structures after printing, as checked via melt-rheology and X-ray scattering. The linear and three-arm star poly(isobutylene)s PIB-B2 (Mn = 8500 g mol −1), PIB-B3 (Mn = 16 000 g mol −1), and linear poly(ethylene glycol)s PEG-B2 (Mn = 900 g mol−1, 8500 g mol −1) are prepared and then probed by melt-rheology to adjust the viscosity to address the proper printing window. The supramolecular PIB polymers show a rubber-like behavior and are able to form self-supported 3D printed objects at room temperature and below, reaching polymer strand diameters down to 200–300 µm. Nanocomposites of PIB-B2 with silica nanoparticles (12 nm, 5–15 wt%) are generated, in turn leading to an improvement of their shape persistence. A blend of the linear polymer PIB-B2 and the three-arm star polymer PIB-B3 (ratio ≈ 3/1 mol) reaches an even higher structural stability, able to build free-standing structures.