Influence of the Degree of Cure in the Bulk Properties of Graphite Nanoplatelets Nanocomposites Printed via Stereolithography

In this work, we report on the fabrication via stereolithography (SLA) of acrylic-based nanocomposites using graphite nanoplatelets (GNPs) as an additive. GNPs are able to absorb UV-Vis radiation, thus blocking partial or totally the light path of the SLA laser. Based on this, we identified a range of GNP concentrations below 2.5 wt %, where nanocomposites can be successfully printed. We show that, even though GNP is well-dispersed along the polymeric matrix, nanocomposites presented lower degrees of cure and therefore worse mechanical properties when compared with pristine resin. However, a post-processing at 60 degrees C with UV light for 1 h eliminates this difference in the degree of cure, reaching values above 90% in all cases. In these conditions, the tensile strength is enhanced for 0.5 wt % GNP nanocomposites, while the stiffness is increased for 0.5-1.0 wt % GNP nanocomposites. Finally, we also demonstrate that 2.5 wt % GNP nanocomposites possess characteristic properties of semiconductors, which allows them to be used as electrostatic dispersion materials

Large Format Additive Manufacturing of Polyethylene terephthalate (PET) by Material Extrusion

Polyethylene terephthalate (PET) is an engineering material widely used in packaging and cosmetics, given its excellent mechanical properties, water resistance and recyclability. PET is typically manufactured by injection blow molding but its use in additive manufacturing (AM) is not spread enough due to its (semi)crystalline behavior, which makes it difficult to process by Material Extrusion (ME) technologies. Alternatively, polyethylene terephthalate glycol copolymer (PETG), a fully amorphous material, is used in these technologies. However, PETG has worse mechanical properties than PET. In this context, this work studies the viability of different commercial PET by ME for Large Format Additive Manufacturing (LFAM). While PET for general purposes (PET1 and PET2) could not be printed, a marketable PET for thick-walled products (PET3) allowed to manufacture different objects by ME-LFAM with good dimensional accuracy. DSC and XRD studies evidenced that its slow crystallizing behavior was key to obtaining a proper flow and a successful printing. Young’s modulus and tensile strength of PET3 was significantly higher than those of PETG, both from this work and in previous reports found in the literature, since it remains semicrystalline after printing. This allows expanding the library of materials available for AM, positioning PET as a potential material for those industrial applications where PETG does not meet the necessary mechanical requirements

Printable Graphene Oxide Nanocomposites as Versatile Platforms for Immobilization of Functional Biomolecules

A series of novel nanocomposites containing graphene oxide (GO) suitable for stereolithography is presented. Different loads of GO are tested, identifying that these materials can be printed with concentrations up to 2.5 wt% GO, presenting improved mechanical properties for concentrations below 1.0 wt% GO. In this range, the nanocomposites exhibit higher strength and toughness when compared to the pristine resin. Microscopic analyses of the material demonstrate that this can be correlated with the good compatibility of GO with the resin, which favors its homogeneous dispersion in the form of flexible nanoplates. After manufacturing, the availability of GO to participate in surface modification reactions with chitosan (CHI) and an alkaline phosphatase (ALP) is evaluated. CHI and ALP are well-known to act as biological cues in biorecognition processes, evidencing that these nanocomposites are suitable as platforms for selective immobilization of functional biomolecules.This work was funded by the Ministry of Science, Innovation and Universities (TEC2017-86102-C2-2-R), the 2014-2020 ERDF Operational Programme and the Department of Economy, Knowledge, Business and University of the Regional Government of Andalusia (FEDER-UCA18-106586). Co-funding from UE and the research group INNANOMAT (ref. TEP-946) is also acknowledged. A.S.d.L. and M.d.l.M. acknowledge Ministry of Science, Innovation and Universities for their Juan de la Cierva Incorporacion postdoctoral fellowships (IJC2019-041128-I, IJCI-2017-31507). SEM and TEM measurements were carried out at the DME-SC-ICyT-ELECMI-UCA

Plasmonic Characterization of 3D Printable Metal-Polymer Nanocomposites

Plasmonic polymer nanocomposites (i.e., polymer matrices containing plasmonic nanostructures) are appealing candidates for the development of manifold technological devices relying on light-matter interactions, provided that they have inherent properties and processing capabilities. The smart development of plasmonic nanocomposites requires in-depth optical analyses proving the material performance, along with correlative studies guiding the synthesis of tailored materials. Importantly, plasmon resonances emerging from metal nanoparticles affect the macroscopic optical response of the nanocomposite, leading to far- and near-field perturbations useful to address the optical activity of the material. We analyze the plasmonic behavior of two nanocomposites suitable for 3D printing, based on acrylic resin matrices loaded with Au or Ag nanoparticles. We compare experimental and computed UV-vis macroscopic spectra (far-field) with single-particle electron energy loss spectroscopy (EELS) analyses (near-field). We extended the calculations of Au and Ag plasmon-related resonances over different environments and nanoparticle sizes. Discrepancies between UV-vis and EELS are dependent on the interplay between the metal considered, the surrounding media, and the size of the nanoparticles. The study allows comparing in detail the plasmonic performance of Au- and Ag-polymer nanocomposites, whose plasmonic response is better addressed, accounting for their intended applications (i.e., whether they rely on far- or near-field interactions)

Influence of Network Topology on the Viscoelastic Properties of Dynamically Crosslinked Hydrogels

Biological materials combine stress relaxation and self-healing with non-linear stress-strain responses. These characteristic features are a direct result of hierarchical self-assembly, which often results in fiber-like architectures. Even though structural knowledge is rapidly increasing, it has remained a challenge to establish relationships between microscopic and macroscopic structure and function. Here, we focus on understanding how network topology determines the viscoelastic properties, i.e., stress relaxation, of biomimetic hydrogels. We have dynamically crosslinked two different synthetic polymers with one and the same crosslink. The first polymer, a polyisocyanopeptide (PIC), self-assembles into semi-flexible, fiber-like bundles, and thus displays stress-stiffening, similar to many biopolymer networks. The second polymer, 4-arm poly(ethylene glycol) (starPEG), serves as a reference network with well-characterized structural and viscoelastic properties. Using one and the same coiled coil crosslink allows us to decouple the effects of crosslink kinetics and network topology on the stress relaxation behavior of the resulting hydrogel networks. We show that the fiber-containing PIC network displays a relaxation time approximately two orders of magnitude slower than the starPEG network. This reveals that crosslink kinetics is not the only determinant for stress relaxation. Instead, we propose that the different network topologies determine the ability of elastically active network chains to relax stress. In the starPEG network, each elastically active chain contains exactly one crosslink. In the absence of entanglements, crosslink dissociation thus relaxes the entire chain. In contrast, each polymer is crosslinked to the fiber bundle in multiple positions in the PIC hydrogel. The dissociation of a single crosslink is thus not sufficient for chain relaxation. This suggests that tuning the number of crosslinks per elastically active chain in combination with crosslink kinetics is a powerful design principle for tuning stress relaxation in polymeric materials. The presence of a higher number of crosslinks per elastically active chain thus yields materials with a slow macroscopic relaxation time but fast dynamics at the microscopic level. Using this principle for the design of synthetic cell culture matrices will yield materials with excellent long-term stability combined with the ability to locally reorganize, thus facilitating cell motility, spreading, and growth

Self-Assembly of CsPbBr3Perovskites in Micropatterned Polymeric Surfaces: Toward Luminescent Materials with Self-Cleaning Properties

In this work, we present a series of porous, honeycomb-patterned polymer films containing CsPbBr3 perovskite nanocrystals as light emitters prepared by the breath figure approach. Microscopy analysis of the topography and composition of the material evidence that the CsPbBr3 nanocrystals are homogeneously distributed within the polymer matrix but preferably confined inside the pores due to the fabrication process. The optical properties of the CsPbBr3 nanocrystals remain unaltered after the film formation, proving that they are stable inside the polystyrene matrix, which protects them from degradation by environmental factors. Moreover, these surfaces present highly hydrophobic behavior due to their high porosity and defined micropatterning, which is in agreement with the Cassie-Baxter model. This is evidenced by performing a proof-of-concept coating on top of 3D-printed LED lenses, conferring the material with self-cleaning properties, while the CsPbBr3 nanocrystals embedded inside the polymeric matrix maintain their luminescent behavior.This work was funded by the Ministry of Science, Innovation and Universities (project TEC2017-86102-C2-2-R) and Junta de Andalucía (Research group INNANOMAT, ref. TEP-946) and co-financed by the 2014-2020 ERDF Operational Programme and by the Department of Economy, Knowledge, Business and University of the Regional Government of Andalusia (ref: FEDER-UCA18-106586). Co-funding from UE is also acknowledged. A.S.d.L. acknowledges the Ministry of Science, Innovation and Universities for his Juan de la Cierva Incorporación postdoctoral fellowship (IJC2019-041128-I). R.A. also acknowledges the support of the Spanish MINECO through projects: Retos-Colaboración 2016 Project Safetag (no. RTC-2016-5197-2) and Retos de la Sociedad Project Nirvana (no. PID2020-119628RB-C31) by MCIN/AEI/10.13039/ 501100011033 and the “Agencia Valenciana de la Innovació” for the Valorització 2018 Project Hidronio (no. INNVAL10/ 18/032) and Valorització 2021 Project CATIOX (no. INNVA1/2021/56). R.A. also thanks the Spanish MINECO for their Ramón y Cajal Fellowship (no. RYC-2015-18349). SEM and TEM measurements were carried out at the DME-SCICyT- ELECMI-UCA

Polymer Composites with Cork Particles Functionalized by Surface Polymerization for Fused Deposition Modeling

Cork powder received as a byproduct from local industries is valorized through the development of composite materials suitable for fused deposition modeling (FDM). For this purpose, a polymeric matrix of acrylonitrile-styrene-butyl acrylate (ASA) is used due to its good mechanical resistance and weather resistance properties. Prior to the manufacturing of the composites, the cork particles are characterized and modified by surface polymerization, creating a layer of poly(butyl acrylate) (PBA). Then, filaments for FDM are prepared by solvent casting and extrusion from ASA and composites with unmodified cork (ASA + C) and PBA-modified cork (ASA + C-m). PBA is one of the polymers present in the structure of ASA, which increases the compatibility between the cork particles and the polymer matrix. This is evidenced by evaluating the mechanical properties of the composites and examining their fracture surface by scanning electron microscopy. The analysis of the thermal properties shows that the developed composites also present enhanced insulating properties.This work was funded by the ADICORK project through a collaboration agreement between Junta de Andalucia (Ministry of Agriculture, Livestock, Fisheries and Sustainable Develop-ment) and the University of Cadiz (research group INNANOMAT, ref . TEP-946) . This agreement has been funded by UE Integrated Territorial Investment (ITI) . A.S.d.L. acknowledges the Ministry of Science, Innovation and Universities for his Juan de la Cierva Incorporacion postdoctoral fellowship (IJC2019-041128-I) . N.F.-D. also acknowledges co-founding by European Social Fund and Ministry of Economic Transformation, Industry, Knowledge and Universities of the Junta de Andalucia. The authors would like to thank Corchos del Estrecho for supplying the cork powder used in this research. SEM measurements were carried out at the DME-SC-ICyT-ELECMI-UCA

Additive Manufacturing of Thermoplastic Polyurethane-Cork Composites for Material Extrusion Technologies

Among the material extrusion technologies of additive manufacturing, fused granular fabrication is playing a bigger role in the industry. The increase in the size of printers demands extrusion systems with higher deposition rates that facilitate printing larger parts in shorter times with a need for cost reduction. This cost reduction in fused granular fabrication systems is due to the utilisation of pellets as the material source for the prints, such as pellets that are the most common way of distributing polymeric materials in industry and do not need the usual previous transformation into filaments. Most of the polymers in the industry can be found in the shape of pellets, so the opportunities for developing new materials beside the traditional filaments found in the market are expanding. In this research, a novel composite material has been developed based on the blending of commercial thermoplastic polyurethane (TPU) and cork particles obtained from industrial waste at different concentrations. These materials have been processed at a laboratory scale, and their mechanical, thermal and rheological properties have been studied. Despite a 53.52% reduction in the maximum stress on the x-axis, an 81.82% decrease in the values obtained with specimens oriented on the z-axis and a shortage in the deformation values, the results reveal a remarkable weight reduction leading to 21.31% when compared to the TPU of the blends,. These results may open a path to further explore these blends and find suitable applications in industry as proposed

Influence of the Carbon Fiber Length Distribution in Polymer Matrix Composites for Large Format Additive Manufacturing via Fused Granular Fabrication

Many studies assess the suitability of fiber-reinforced polymer composites in additive manufacturing. However, the influence of the fiber length distribution on the mechanical and functional properties of printed parts using these technologies has not been addressed so far. Hence, in this work we compare different composites based on Acrylonitrile Styrene Acrylate (ASA) and carbon fiber (CF) suitable for large format additive manufacturing (LFAM) technologies based on fused granular fabrication (FGF). We study in detail the influence of the CF size on the processing and final properties of these materials. Better reinforcements were achieved with longer CF, reaching Young’s modulus and tensile strength values of 7500 MPa and 75 MPa, respectively, for printed specimens. However, the longer CF also worsened the interlayer adhesion of ASA to a greater extent. The composites also exhibited electrical properties characteristic of electrostatic dissipative (ESD) materials (105–1010 Ω/sq) and low coefficients of thermal expansion below 15 µm/m·°C. These properties are governed by the CF length distribution, so this variable may be used to tune these values. These composites are promising candidates for the design of elements with enhanced mechanical and functional properties for ESD protection elements or molds, so the products can be manufactured on demand.Ministerio de Ciencia, Innovación y Universidades (España) Junta de Andalucía (España)13 página

Itaconic-Acid-Based Sustainable Poly(ester amide) Resin for Stereolithography

Material science is recognized as a frontrunner in achieving a sustainable future, owing to its primary reliance upon petroleum-based chemical raw materials. Several efforts are made to implement common renewable feedstocks as an alternative to common fossil resources. For this purpose, additive manufacturing (AM) represents promising and effective know-how for the replacement of high energy- and resource-demanding processes with more environmentally friendly practices. This work presents a novel biobased ink for stereolithography, which has been formulated by mixing a photocurable poly(ester amide) (PEA) obtained from renewable resources with citrate and itaconate cross-linkers and appropriate photopolymerization initiators, terminators, and dyes. The mechanical features and the relative biocompatibility of 3D-printed objects have been carefully studied to evaluate the possible resin implementation in the field of the textile fashion industry.9 página