Effects of Accelerating the Ageing of 1D PLA Filaments after Fused Filament Fabrication.

The effects of post-treatment temperature-based methods for accelerating the ageing of PLA were studied on 1D single-PLA filaments after fused filament fabrication (FFF). The goal was to answer the questions whether the PLA can be safely aged-i.e., without degrading-at higher temperatures; at which temperatures, if any; how long it takes for the PLA to fully age at the chosen temperature; and which are the main differences between the material aged at room temperature and the material aged at higher temperatures. We also share other helpful information found. The use of 1D filaments allows for decoupling the variables related to the 3D structure (layer height, raster angle, infill density, and layers adhesion) from the variables solely related to the material (here, we analysed the molecular weight, the molecular orientation, and the crystallinity). 1D PLA filaments were aged at 20, 39, 42, 51, 65, 75, and 80 °C in a water-bath-inspired process in which the hydrolytic degradation of the PLA was minimised for the ageing temperatures of interest. Those temperatures were selected based on a differential scanning calorimetry (DSC) scan of the PLA right after it was printed in order to study the most effective ageing temperature, 39 °C, and highlight possible degradation mechanisms during ageing. The evolution of the thermal and mechanical properties of the PLA filaments at different temperatures was recorded and compared with those of the material aged at room temperature. A DSC scan was used to evaluate the thermal and physical properties, in which the glass transition, enthalpic relaxation, crystallisation, and melting reactions were analysed. A double glass transition was found, and its potential implications for the scientific community are discussed. Tensile tests were performed to evaluate the tensile strength and elastic modulus. The flow-induced molecular orientation, the degradation, the logistic fitting, and the so-called summer effect-the stabilisation of properties at higher values when aged at higher temperatures-are discussed to assess the safety of accelerating the ageing rate and the differences between the materials aged at different temperatures. It was found that the PLA aged at 39 °C (1) reached almost stable properties with just one day of ageing, i.e., the ageing rate accelerated by 875% for the elastic modulus and by 1635% for the yield strength; (2) the stable properties were higher than those from the PLA aged at room temperature; and (3) no signs of degradation were identified for the ageing temperature of interest.

On the Mechanical Properties of Hybrid Dental Materials for CAD/CAM Restorations.

Two hybrid dental materials available for computer-aided design and manufacturing (CAD/CAM) dental restorations have been selected to explore their potential. On the one hand, the scarcely investigated polymer-based material Vita Enamic® (VE) and, on the other hand, the leucite-based material IPS Empress® CAD (EC). Their micro-structure and mechanical performance were analyzed in two environments: directly as received by the manufacturer (AR), and after immersion and storage in artificial saliva (AS) for 30 days to determine the influence of the saliva effect. To avoid an inappropriate selection of materials for clinical use, a full understanding of their mechanical behavior is essential. Therefore, this investigation aims to determine the micro-structural and chemical composition by field emission scanning electron microscopy (FE-SEM) and X-ray fluorescence analysis, establishing the density, micro- and nano-hardness, the nano-elastic modulus, and the flexural strength and fracture toughness (by introducing a femto-laser notch to replicate a real crack). In addition, fracture surfaces of the broken samples were analyzed to correlate the failure micro-mechanisms with their mechanical properties. Results indicate that while the crystalline phase of the materials is very similar (composed of SiO2 and Al2O3), the micro-structure and mechanical behavior is not. The material EC, with finer micro-structure, exhibits a higher mechanical performance but with greater variability of results. Furthermore, the material VE, with a 25 vol.% polymer phase, shows a mechanical performance similar to enamel and dentin and therefore more similar to human behavior.

Natural Ageing of PLA Filaments, Can It Be Frozen?

The physical ageing of polylactic acid (PLA) is a phenomenon that changes the material's properties over time. This ageing process is highly dependent on ambient variables, such as temperature and humidity. For PLA, the ageing is noticeable even at room temperatures, a process commonly referred to as natural ageing. Stopping the ageing by freezing the material can be helpful to preserve the properties of the PLA and stabilise it at any time during its storage until it is required for testing. However, it is essential to demonstrate that the PLA's mechanical properties are not degraded after defrosting the samples. Four different methods for stopping the ageing (anti-ageing processes) are analysed in this paper-all based on freezing and defrosting the PLA samples. We determine the temperature and ambient water vapor influence during the freezing and defrosting process using desiccant and zip bags. The material form selected is PLA filaments (no bulk material or scaffold structures) printed at 190 °C with diameters between 400 and 550 µm and frozen at -24 °C in the presence or absence of a desiccant. The impact of the anti-ageing processes on PLA's ageing and mechanical integrity is studied regarding the thermal, mechanical and fractographical properties. In conclusion, an anti-ageing process is defined to successfully stop the natural ageing of the PLA for an indefinite length of time. This process does not affect the mechanical properties or the structural integrity of the PLA. As a result, large quantities of this material can be produced in a single batch and be safely stored to be later characterised under the same manufacturing and ageing conditions, which is currently a limiting factor from an experimental point of view as polymeric filament properties can show significant variety from batch to batch.

The Mechanical, Thermal, and Chemical Properties of PLA-Mg Filaments Produced via a Colloidal Route for Fused-Filament Fabrication.

The effect of Mg particles on the thermal, chemical, physical, and primarily mechanical properties of 3D-printed PLA/Mg composites is studied in this paper. Recently, new colloidal processing has been proposed to introduce Mg particles into the PLA matrix, which ensures good dispersion of the particles and better thermal properties, allowing for thermal processing routes such as extrusion or 3D printing via fused-filament fabrication. The thermal and physical properties are here studied in 1D single-filament-printed PLA/Mg composites with 0 to 10 wt.% of Mg particles by Differential Scanning Calorimetry (DSC); we analyse the PLA chain modifications produced, the crystallinity fraction, and the different crystalline forms of the PLA after thermal processing. Fourier Transform Infrared Spectroscopy (FTIR) is used to confirm the influence of the PLA/Mg colloidal processing after printing. The mechanical properties are measured with a universal tensile test machine on the 1D single-printed filaments via fused-filament fabrication (FFF); the filaments were naturally aged to stable conditions. Filaments with and without a notch are studied to obtain the materials' tensile strength, elastic modulus, and fracture toughness. Different analytical models to explain the results of the PLA-Mg were studied, in which the minimum values for the interface strength of the PLA-Mg composites were calculated.

Saliva Influence on the Mechanical Properties of Advanced CAD/CAM Composites for Indirect Dental Restorations.

This study aims to evaluate the microstructural and mechanical properties of three commercial resin-based materials available for computer-aid design and manufacturing (CAD/CAM)-processed indirect dental restoration: LavaTM Ultimate Restorative (LU), 3M ESPE; Brilliant Crios (BC), COLTENE and CerasmartTM (CS), GC Dental Product. The three types of resin-based composite CAD/CAM materials were physically and mechanically tested under two conditions: directly as received by the manufacturer (AR) and after storage under immersion in artificial saliva (AS) for 30 days. A global approximation to microstructure and mechanical behaviour was evaluated: density, hardness and nanohardness, nanoelastic modulus, flexural strength, fracture toughness, fracture surfaces, and microstructures and fractography. Moreover, their structural and chemical composition using X-ray fluorescence analysis (XRF) and field emission scanning electron microscopy (FESEM) were investigated. As a result, LU exhibited slightly higher mechanical properties, while the decrease of its mechanical performance after immersion in AS was doubled compared to BC and CS. Tests of pristine material showed 13 GPa elastic modulus, 150 MPa flexural strength, 1.0 MPa·m1/2 fracture toughness, and 1.0 GPa hardness for LU, 11.4 GPa elastic modulus; 140 MPa flexural strength, 1.1 MPa·m1/2 fracture toughness, and 0.8 GPa hardness for BC; and 8.3 GPa elastic modulus, 140 MPa flexural strength, 0.9 MPa·m1/2 fracture toughness, and 0.7 GPa hardness for CS. These values were significantly reduced after one month of immersion in saliva. The interpretation of the mechanical results could suggest, in general, a better behaviour of LU compared with the other two despite it having the coarsest microstructure of the three studied materials. The saliva effect in the three materials was critically relevant for clinical use and must be considered when choosing the best solution for the restoration to be used.

Influence of HRGO Nanoplatelets on Behaviour and Processing of PMMA Bone Cement for Surgery.

Bone cement, frequently based on poly (methyl methacrylate), is commonly used in different arthroplasty surgical procedures and its use is essential for prosthesis fixation. However, its manufacturing process reaches high temperatures (up to 120 °C), producing necrosis in the patients' surrounding tissues. To help avoid this problem, the addition of graphene could delay the polymerisation of the methyl methacrylate as it could, simultaneously, favour the optimisation of the composite material's properties. In this work, we address the effect of different percentages of highly reduced graphene oxide with different wt.% (0.10, 0.50, and 1.00) and surface densities (150, 300, 500, and 750 m2/g) on the physical, mechanical, and thermal properties of commercial poly (methyl methacrylate)-based bone cement and its processing. It was noted that a lower sintering temperature was achieved with this addition, making it less harmful to use in surgery and reducing its adverse effects. In contrast, the variation of the density of the materials did not introduce significant changes, which indicates that the addition of highly reduced graphene oxide would not significantly increase bone porosity. Lastly, the mechanical properties (strength, elastic modulus, and fracture toughness) were reduced by almost 20%. Nevertheless, their typical values are high enough that these new materials could still fulfil their structural function. In conclusion, this paper presents a way to control the sintering temperature, without significant degradation of the mechanical performance, by adding highly reduced graphene oxide so that local necrosis of bone cement based on poly (methyl methacrylate) used in surgery is avoided.

Characterisation and Modelling of PLA Filaments and Evolution with Time.

The properties of polylactic acid (PLA) filaments have not yet been analysed in detail, and they are strongly affected by the extrusion process used in some additive manufacturing systems. Here we present the mechanical, thermal, physical, and fractographical properties of an extruded filament (not the bulk material or scaffolds), the basic building block of any PLA structure printed via material extrusion. This research aims to create a reference point for the modelisation of additively manufactured structures via extrusion processes, as the main building block is characterised in detail for a deep understanding. Furthermore, we investigated the natural ageing (up to one year), the effect of the printing (extruding) temperature (180 and 190 °C), and the effect of the crosshead speed during the tensile tests (10-1 to 102 mm/min) to provide a deeper analysis of the material. The results showed that the material extruded at 190 °C performed better than the material extruded at 180 °C. However, after one hundred days of natural ageing, both materials behaved similarly. This was related to the flow-induced molecular orientation during the extrusion. The crosshead rate produced a logarithmic increase of the mechanical properties, consistent with the Eyring model. Additionally, the ageing produced significant changes in both the elastic modulus and the yield strength: from 2.4 GPa and 40 MPa, in one-day-aged samples, up to 4 GPa and 62 MPa once entirely aged. Finally, it was observed that the glass transition and the enthalpic relaxation increased with ageing, agreeing with the Kohlraushch-William-Watts model.

Influence of lactose addition to gentamicin-loaded acrylic bone cement on the kinetics of release of the antibiotic and the cement properties.

The purpose of this study was to characterize a poly(methyl methacrylate) bone cement that was loaded with the antibiotic gentamicin sulphate (GS) and lactose, which served to modulate the release of GS from cement specimens. The release of GS when the cement specimens were immersed in phosphate-buffered saline at 37 degrees Celsius was determined spectrophotometrically. The microstructure, porosity, density, tensile properties and flexural properties of the cements were determined before and after release of GS. A kinetics model of the release of GS from the cement that involved a coupled mechanism based on dissolution/diffusion processes and an initial burst effect was proposed. Dissolution assay results showed that drug elution was controlled by a diffusion mechanism which can be modulated by lactose addition. Density values and mechanical properties (tensile strength, flexural strength, elastic modulus and fracture toughness) were reduced by the increased porosity resulting from lactose addition, but maintained acceptable values for the structural functions of bone cement. The present results suggest that lactose-modified, gentamicin-loaded acrylic bone cements are potential candidates for use in various orthopaedic and dental applications.