Comparative Screening of the Structural and Thermomechanical Properties of FDM Filaments Comprising Thermoplastics Loaded with Cellulose, Carbon and Glass Fibers.

Additive manufacturing (AM) has been rapidly growing for a decade in both consumer and industrial products. Fused deposition modeling (FDM), one of the most widely used additive manufacturing methods, owes its popularity to cost effectiveness in material and equipment investment. Current efforts are aimed toward high load-bearing capacity at low material costs. However, the mechanical reliability of end-products derived from these compositions and their dependence on microstructural effects, have remained as major limitations. This is mainly owing to the unknown mechanics of the materials, including the reinforcing or filler components and their interphase/interface compatibility. For this reason, here we investigate the most relevant commercial polymeric materials used in composite filaments, associated phases and the characterization protocols that can guide component selection, screening and troubleshooting. We first present thermal analyses (thermogravimetric, TGA and differential scanning calorimetry, DSC) in relation to the constituent fractions and identify the type of polymer for uses in filaments production. The influence of various fillers is unveiled in terms of the crystallization behavior of derived 3D-printed parts. To understand the microstructural effects on the material strength, we carry out a series of tensile experiments on 3-D printed dog-bone shaped specimens following ISO standards. Simultaneously, real-time thermal energy dissipation and damage analyses are applied by using infrared measurements at fast frame rates (200 Hz) and high thermal resolution (50 mK). The failure regions of each specimen are examined via optical, scanning and transmission electron microscopies. The results are used to reveal new insights into the size, morphology and distribution of the constituents and interphases of polymer filaments for FDM. The present study represents advancement in the field of composite filament fabrication, with potential impact in the market of additive manufacturing.

Films based on crosslinked TEMPO-oxidized cellulose and predictive analysis via machine learning.

We systematically investigated the effect of film-forming polyvinyl alcohol and crosslinkers, glyoxal and ammonium zirconium carbonate, on the optical and surface properties of films produced from TEMPO-oxidized cellulose nanofibers (TOCNFs). In this regard, UV-light transmittance, surface roughness and wetting behavior of the films were assessed. Optimization was carried out as a function of film composition following the "random forest" machine learning algorithm for regression analysis. As a result, the design of tailor-made TOCNF-based films can be achieved with reduced experimental expenditure. We envision this approach to be useful in facilitating adoption of TOCNF for the design of emerging flexible electronics, and related platforms.

From colloidal spheres to nanofibrils: extensional flow properties of mineral pigment and mixtures with micro and nanofibrils under progressive double layer suppression.

Suspensions of mineral pigment and cellulose fibrillar derivatives are materials regularly found in the forest products industries, particularly in paper and board production. Many manufacturing processes, including forming and coating employ flow geometries incorporating extensional flow. Traditionally, colloidal mineral pigment suspensions have been considered to show little to no non-linear behaviour in extensional viscosity. Additionally, recently, nanofibrillar materials, such as microfibrillar (MFC) and nanofibrillar cellulose (NFC), collectively termed MNFC, have been confirmed by their failure to follow the Cox-Merz rule to behave more as particulate material rather than showing polymeric rheological properties when dispersed in water. Such suspensions and their mixtures are currently intensively investigated to enable them to generate likely enhanced composite material properties. The processes frequently involve exposure to increasing levels of ionic strength, coming either from the weak solubility of pigments, such as calcium carbonate, or retained salts arising from the feed fibre source processing. By taking the simple case of polyacrylate stabilised calcium carbonate suspension and comparing the extensional viscosity as a function of post extension capillary-induced Hencky strain on a CaBER extensional rheometer over a range of increasing salt concentration, it has been shown that the regime of constriction changes as the classic DLVO double layer is progressively suppressed. This change is seen to lead to a characteristic double (bimodal) measured viscosity response for flocculated systems. With this novel characteristic established, more complex mixed suspensions of calcium carbonate, clay and MNFC have been studied, and the effects of fibrils versus flocculation identified and where possible separated. This technique is suggested to enable a better understanding of the origin of viscoelasticity in these important emerging water-based suspensions.

Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil.

We demonstrate that superhydrophobic and superoleophobic nanocellulose aerogels, consisting of fibrillar networks and aggregates with structures at different length scales, support considerable load on a water surface and also on oils as inspired by floatation of insects on water due to their superhydrophobic legs. The aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Furthermore, we demonstrate high-adhesive pinning of water and oil droplets, gas permeability, light reflection at the plastron in water and oil, and viscous drag reduction of the fluorinated aerogel in contact with oil. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.