Development of carbon fiber acrylonitrile styrene acrylate composite for large format additive manufacturing

The increasing interest of Large Format Additive Manufacturing (LFAM) technologies in various industrial sectors mainly lies on the attainable production of pieces reaching several cubic meters. These new technologies require the development of optimized materials with two-folded capabilities, able to satisfy functional in-service requirements but also showing a proper printability. Acrylonitrile Styrene Acrylate (ASA) is among the most interesting thermoplastic materials to be implemented in a LFAM device due to its excellent wettability and mechanical properties. This research focuses on the development and characterization of ASA and carbon fiber (CF) ASA composites suitable for LFAM. The rheological, thermal and mechanical properties of neat ASA and ASA containing 20 wt% CF are addressed. The results evidence the higher performance of the CF loaded composite compared to the raw ASA polymer (i.e., the 20 wt% CF composite shows a 350% increase in flexural Young's Modulus and a 500% increment in thermal conductivity compared with neat ASA). Additionally, both materials were successfully printed along perpendicular directions (X and Z), showing the maximum tensile strain for the composite printed along the X orientation as was expected. The results of the flexural tests are comparable or slightly higher than those of injected parts. Finally, the fracture surface was analysed, identifying different types of porosity

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

Basalt Fiber Composites with Reduced Thermal Expansion for Additive Manufacturing

Fused filament fabrication (FFF) is gaining attention as an efficient way to create parts and replacements on demand using thermoplastics. This technology requires the development of new materials with a reliable printability that satisfies the requirement of final parts. In this context, a series of composites based on acrylonitrile styrene acrylate (ASA) reinforced with basalt fiber (BF) are reported in this work. First, several surface modification treatments are applied onto the BF to increase their compatibility with the ASA matrix. Then, once the best treatment is identified, the mechanical properties, coefficient of thermal expansion (CTE) and warping distortion of the different specimens designed and prepared by FFF are studied. It was found that the silanized BF is appropriate for an adequate printing, obtaining composites with higher stiffness, tensile strength, low CTE and a significant reduction in part distortion. These composites are of potential interest in the design and manufacturing of final products by FFF, as they show much lower CTE values than pure ASA, which is essential to successfully fabricate large objects using this technique

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

Five years of designing wireless sensor networks in the Doñana Biological Reserve (Spain): an applications approach

Wireless Sensor Networks (WSNs) are a technology that is becoming very popular for many applications, and environmental monitoring is one of its most important application areas. This technology solves the lack of flexibility of wired sensor installations and, at the same time, reduces the deployment costs. To demonstrate the advantages of WSN technology, for the last five years we have been deploying some prototypes in the Doñana Biological Reserve, which is an important protected area in Southern Spain. These prototypes not only evaluate the technology, but also solve some of the monitoring problems that have been raised by biologists working in Doñana. This paper presents a review of the work that has been developed during these five years. Here, we demonstrate the enormous potential of using machine learning in wireless sensor networks for environmental and animal monitoring because this approach increases the amount of useful information and reduces the effort that is required by biologists in an environmental monitoring task

Deletion patterns, genetic variability and protein structure of pfhrp2 and pfhrp3: implications for malaria rapid diagnostic test in Amhara region, Ethiopia

Background: Although rapid diagnostic tests (RDTs) play a key role in malaria-control strategies, their efficacy has been threatened by deletion and genetic variability of the genes pfhrp2/3. This study aims to characterize the deletion, genetic patterns and diversity of these genes and their implication for malaria RDT effectiveness, as well as their genetic evolution in the Amhara region of Ethiopia. Methods: The study included 354 isolates from symptomatic patients from the Amhara region of Ethiopia who tested positive by microscopy. Exon 1?2 and exon 2 of genes pfhrp2 and -3 were amplified, and exon 2 was sequenced to analyse the genetic diversity, phylogenetic relationship and epitope availability. Results: The deletion frequency in exon 1?2 and exon 2 was 22 and 4.6% for pfhrp2, and 68 and 18% for pfhrp3, respectively. Double deletion frequency for pfhrp2 and pfhrp3 was 1.4%. High genetic diversity, lack of clustering by phylogenetic analysis and evidence of positive selection suggested a diversifying selection for both genes. The amino-acid sequences, classified into different haplotypes, varied widely in terms of frequency of repeats, with novel amino-acid changes. Aminoacidic repetition type 2 and type 7 were the most frequent in all the sequences. The most frequent epitopes among protein sequences were those recognized by MAbs 3A4 and C1-13. Conclusion: Deletions and high amino acidic variation in pfhrp2 and pfhrp3 suggest their possible impact on RDT use in the Amhara region, and the high genetic diversity of these genes could be associated with a diversifying selection in Ethiopia. Surveillance of these genes is, therefore, essential to ensure the effectiveness of public health interventions in this region.Instituto de Salud Carlos II

Induced damage during STEM-EELS analyses on acrylic-based materials for Stereolithography

(Scanning) transmission electron microscopy, (S)TEM, offers a powerful characterization tool based on electron-matter interactions, highly valuable in materials science. However, the possible electron beam induced damage during (S)TEM measurements hinders the analysis of soft materials, such as acrylic resins. Importantly, acrylic resins offer an appealing playground for the development of novel composites with customized properties and convenient processing capabilities for 3D-printing technologies, including Stereolithography (SLA). There are several factors preventing the optimal performance of TEM measurements applied to acrylic resins, among which we focus on the quality of the analyzed specimen (i.e., compromise between thickness and robustness, to achieve electron transparency while keeping the material integrity), particularly challenging when working with soft materials; the electrostatic charging/discharging effects, resulting in sample drift and related noise/artefacts; and the radiolysis and knock-on electron-induced damage, which directly degrade the material under study. We explore and compare different methodologies to obtain resin specimens suitable for (S)TEM analysis, employed for the subsequent study of the electron–beam damage induced during STEM-EELS measurements. Furthermore, we propose likely underlying mechanisms explaining the acrylic resin degradation based on the different EELS monitored signals. On one hand, we assess the evolution of the carbon and oxygen content, as well as the material thinning as a function of the accumulated electron dose. On the other hand, we extract meaningful information from the spectral shape of carbon and oxygen K-edges upon increasing electron doses, unraveling likely degradation pathways. The earned understanding on the electron-beam induced damage and the determination of critical doses provide a useful framework for the implementation of (S)TEM techniques as useful tools to help in the smart engineering of acrylic-based composites for SLA.DME-SC-ICyT-ELECMI-UCAUnión Europea - Junta de Andalucía - INNANOMAT TEP94

Synthesis and Characterisation of ASA-PEEK Composites for Fused Filament Fabrication

In this paper, a series of polymer composites made from acrylonitrile-styrene-acrylate (ASA) and poly (ether ether ketone) (PEEK) were manufactured. ASA acts as a polymer matrix while PEEK is loaded in the form of micro-particles that act as a reinforcing filler. The composites were compounded by single screw extrusion and then, different specimens were manufactured either via injection moulding (IM) or fused filament fabrication (FFF). Two different types of PEEK (commercial and reused) in different concentrations (3 and 6 wt.%) were tested and their influence in the mechanical, structural, and thermal properties were studied. It was observed that reused PEEK enhanced the stiffness and tensile strength and thermal stability of the composites both, for injected and printed specimens. This evidences the suitability of these composites as potential candidates as novel materials with enhanced properties following an approach of circular economy

Stereolithography of Semiconductor Silver and Acrylic-Based Nanocomposites

Polymer nanocomposites (PNCs) attract the attention of researchers and industry because of their potential properties in widespread fields. Specifically, electrically conductive and semiconductor PNCs are gaining interest as promising materials for biomedical, optoelectronic and sensing applications, among others. Here, metallic nanoparticles (NPs) are extensively used as nanoadditives to increase the electrical conductivity of mere acrylic resin. As the in situ formation of metallic NPs within the acrylic matrix is hindered by the solubility of the NP precursors, we propose a method to increase the density of Ag NPs by using different intermediate solvents, allowing preparation of Ag/acrylic resin nanocomposites with improved electrical behaviour. We fabricated 3D structures using stereolithography (SLA) by dissolving different quantities of metal precursor (AgClO4) in methanol and in N,N-dimethylformamide (DMF) and adding these solutions to the acrylic resin. The high density of Ag NPs obtained notably increases the electrical conductivity of the nanocomposites, reaching the semiconductor regime. We analysed the effect of the auxiliary solvents during the printing process and the implications on the mechanical properties and the degree of cure of the fabricated nanocomposites. The good quality of the materials prepared by this method turn these nanocomposites into promising candidates for electronic applications

Efficacy and Safety of a Novel Submucosal Injection Solution for Resection of Gastrointestinal Lesions

Endoscopic mucosal resection (EMR) and endoscopic submucosal dissection (ESD) are minimally invasive and efficient techniques for the removal of gastrointestinal (GI) mucosal polyps. In both techniques, submucosal injection solutions are necessary for complete effectiveness and safety during the intervention to be obtained. The main objective of this study was to evaluate the efficacy and safety of a new sterile submucosal injection solution for EMR/ESD used within a clinical protocol in patients with intestinal polyps. We carried out a prospective study between 2016 and 2017 with patients who attended the Endoscopy Consultation—Digestive Department of Primary Hospital. Patients were selected for EMR/ESD after the application of clinical protocols. Thirty-six patients were selected (≥ 66 years with comorbidities and risk factors). Lesions were located mainly in the colon. Our solution presented an intestinal lift ≥ 60 min in EMR/ESD and a high expansion of tissue, optimum viscosity, and subsequent complete resorption. The genes S100A9 and TP53 presented an expression increase in the distal regions. TP53 and PCNA were the only genes whose expression was increased in polyp specimens vs. the surrounding tissue at the mRNA level. In EMR/ESD, our solution presented a prolonged effect at the intestinal level during all times of the intervention. Thus, our solution seems be an effective and safe alternative in cases of flat lesions in both techniques.Study co-financed by the Junta de Andalucia (PIN-0479-2016, CTS676, CTS235, CTS164), the Ministry of Economy and Competitivity, Spain (SAF2017-88457-R, AGL2017-85270-R), Nakafarma S.L and CIBERehd is funded by Instituto de Salud Carlos III, Spain. The sponsors had no role in the design, execution, interpretation, or writing of the study