Direct ink writing advances in multi-material structures for a sustainable future

Novel manufacturing techniques such as additive manufacturing (AM, also referred to as 3D printing) will play a critical role in building a sustainable future. AM will reduce waste, energy consumption and production time by eliminating the need to assemble components. It will also enable the mass customization of complex devices. To reach their full potential, additive manufacturing technologies should be able to combine different materials in a single processing step. Although the development of multi-material printing is in its infancy, it could have a massive impact in fields as diverse as energy storage and generation, electronic devices, healthcare or structural composites to name a few. Here we provide a critical perspective on the advances and potential of multi-material printing using direct extrusion-based printing, also known as direct ink writing (DIW) or robocasting. We will show examples of devices and structures combining a wide range of materials from ceramics to metals, polymers and carbon with particular focus on three promising applications: energy storage, lightweight composites and sensors. The goals are to assess the progress made so far, to point out specific challenges and areas for further development and to provide guidelines to those interested in multi-material DIW

Mechanical and biological evaluation of 3D printed 10CeTZP-Al2O3 structures

Three-dimensional structures were robocasted from a 10 mol% ceria-stabilized zirconia and alumina composite (10CeTZP-AlO). A hydrogel-based printable ink was developed using a unique non-ionic copolymer surfactant. Self-supporting and free-standing structures, including round lattices with interconnected pores (200–600 μm pores; 30–50% porosity), rectangular bars (95% density on average) and cones were successfully printed. The round lattices of 200 μm pores and 30% porosity showed compression strengths similar to those of cortical bone, reaching almost 200 MPa. The maximum flexural strength value attained for the rectangular bars was 575 MPa. In vitro biological studies demonstrated that the samples allow for practically 100% cell viability, confirming their non-cytotoxic nature. Cell differentiation tests were performed using osteoblasts incubated for 7 days in supplemented cell culture medium. Quantification of specific osseous differentiation genes showed that the robocasted structures induced a higher degree of osseous differentiation than tissue culture polystyrene.This research has been supported by the Spanish Ministry of Science and Innovation (MICINN) and the Spanish Higher Council for Scientific Research (CSIC) under the Project MAT2012-38645. Likewise, the work was partially carried out within the framework of the Regulation of the Government of the Russian Federation dated 9 April 2010 No. 220 (Agreement No. 14.B25.31.0012 dated 26 June 2013). Lidia Goyos-Ball acknowledges financial support from the JAE-PREDOC program (CSIC). Esther García-Tuñón and Eduardo Saiz would like to acknowledge the EPSRC Grant graphene 3D networks (EP/K01658X/1).Peer Reviewe

An Investigation of the Mineral in Ductile and Brittle Cortical Mouse Bone

Bone is a strong and tough material composed of apatite mineral, organic matter, and water. Changes in composition and organization of these building blocks affect bone's mechanical integrity. Skeletal disorders often affect bone's mineral phase, either by variations in the collagen or directly altering mineralization. The aim of the current study was to explore the differences in the mineral of brittle and ductile cortical bone at the mineral (nm) and tissue (µm) levels using two mouse phenotypes. Osteogenesis imperfecta model, oim(-/-) , mice have a defect in the collagen, which leads to brittle bone; PHOSPHO1 mutants, Phospho1(-/-) , have ductile bone resulting from altered mineralization. Oim(-/-) and Phospho1(-/-) were compared with their respective wild-type controls. Femora were defatted and ground to powder to measure average mineral crystal size using X-ray diffraction (XRD) and to monitor the bulk mineral to matrix ratio via thermogravimetric analysis (TGA). XRD scans were run after TGA for phase identification to assess the fractions of hydroxyapatite and β-tricalcium phosphate. Tibiae were embedded to measure elastic properties with nanoindentation and the extent of mineralization with backscattered electron microscopy (BSE SEM). Results revealed that although both pathology models had extremely different whole-bone mechanics, they both had smaller apatite crystals, lower bulk mineral to matrix ratio, and showed more thermal conversion to β-tricalcium phosphate than their wild types, indicating deviations from stoichiometric hydroxyapatite in the original mineral. In contrast, the degree of mineralization of bone matrix was different for each strain: brittle oim(-/-) were hypermineralized, whereas ductile Phospho1(-/-) were hypomineralized. Despite differences in the mineralization, nanoscale alterations in the mineral were associated with reduced tissue elastic moduli in both pathologies. Results indicated that alterations from normal crystal size, composition, and structure are correlated with reduced mechanical integrity of bone

Inflammatory mediators in breast cancer: Coordinated expression of TNFα & IL-1β with CCL2 & CCL5 and effects on epithelial-to-mesenchymal transition

<p>Abstract</p> <p>Background</p> <p>The inflammatory chemokines CCL2 (MCP-1) & CCL5 (RANTES) and the inflammatory cytokines TNFα & IL-1β were shown to contribute to breast cancer development and metastasis. In this study, we wished to determine whether there are associations between these factors along stages of breast cancer progression, and to identify the possible implications of these factors to disease course.</p> <p>Methods</p> <p>The expression of CCL2, CCL5, TNFα and IL-1β was determined by immunohistochemistry in patients diagnosed with: (1) Benign breast disorders (=healthy individuals); (2) Ductal Carcinoma <it>In Situ </it>(DCIS); (3) Invasive Ducal Carcinoma without relapse (IDC-no-relapse); (4) IDC-with-relapse. Based on the results obtained, breast tumor cells were stimulated by the inflammatory cytokines, and epithelial-to-mesenchymal transition (EMT) was determined by flow cytometry, confocal analyses and adhesion, migration and invasion experiments.</p> <p>Results</p> <p>CCL2, CCL5, TNFα and IL-1β were expressed at very low incidence in normal breast epithelial cells, but their incidence was significantly elevated in tumor cells of the three groups of cancer patients. Significant associations were found between CCL2 & CCL5 and TNFα & IL-1β in the tumor cells in DCIS and IDC-no-relapse patients. In the IDC-with-relapse group, the expression of CCL2 & CCL5 was accompanied by further elevated incidence of TNFα & IL-1β expression. These results suggest progression-related roles for TNFα and IL-1β in breast cancer, as indeed indicated by the following: (1) Tumors of the IDC-with-relapse group had significantly higher persistence of TNFα and IL-1β compared to tumors of DCIS or IDC-no-relapse; (2) Continuous stimulation of the tumor cells by TNFα (and to some extent IL-1β) has led to EMT in the tumor cells; (3) Combined analyses with relevant clinical parameters suggested that IL-1β acts jointly with other pro-malignancy factors to promote disease relapse.</p> <p>Conclusions</p> <p>Our findings suggest that the coordinated expression of CCL2 & CCL5 and TNFα & IL-1β may be important for disease course, and that TNFα & IL-1β may promote disease relapse. Further <it>in vitro </it>and <it>in vivo </it>studies are needed for determination of the joint powers of the four factors in breast cancer, as well as analyses of their combined targeting in breast cancer.</p

3D printing with 2D colloids: designing rheology protocols to predict 'printability' of soft-materials

Additive manufacturing (AM) techniques and so-called 2D materials have undergone an explosive growth in the past decade. The former opens multiple possibilities in the manufacturing of multifunctional complex structures, and the latter on a wide range of applications from energy to water purification. Extrusion-based 3D printing, also known as Direct Ink Writing (DIW), robocasting, and often simply 3D printing, provides a unique approach to introduce advanced and high-added-value materials with limited availability into lab-scale manufacturing. On the other hand, 2D colloids of graphene oxide (GO) exhibit a fascinating rheology and can aid the processing of different materials to develop ‘printable’ formulations. This work provides an in-depth rheological study of GO suspensions with a wide range of behaviours from Newtonian-like to viscoelastic ‘printable’ soft solids. The combination of extensional and shear rheology reveals the network formation process as GO concentration increases from <0.1 vol% to 3 vol%. Our results also demonstrate that the quantification of ‘printability’ can be based on three rheology parameters: the stiffness of the network via the storage modulus (G′), the solid-to-liquid transition or flow stress (σf), and the flow transition index, which relates the flow and yield stresses (FTI = σf/σy)