Tailoring diamondised nanocarbon-loaded poly(lactic acid) composites for highly electroactive surfaces: extrusion and characterisation of filaments for improved 3D-printed surfaces.

A new 3D-printable composite has been developed dedicated to electroanalytical applications. Two types of diamondised nanocarbons - detonation nanodiamonds (DNDs) and boron-doped carbon nanowalls (BCNWs) - were added as fillers in poly(lactic acid) (PLA)-based composites to extrude 3D filaments. Carbon black served as a primary filler to reach high composite conductivity at low diamondised nanocarbon concentrations (0.01 to 0.2 S/cm, depending on the type and amount of filler). The aim was to thoroughly describe and understand the interactions between the composite components and how they affect the rheological, mechanical and thermal properties, and electrochemical characteristics of filaments and material extrusion printouts. The electrocatalytic properties of composite-based electrodes, fabricated with a simple 3D pen, were evaluated using multiple electrochemical techniques (cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy). The results showed that the addition of 5 wt% of any of the diamond-rich nanocarbons fillers significantly enhanced the redox process kinetics, leading to lower redox activation overpotentials compared with carbon black-loaded PLA. The detection of dopamine was successfully achieved through fabricated composite electrodes, exhibiting lower limits of detection (0.12 µM for DND and 0.18 µM for BCNW) compared with the reference CB-PLA electrodes (0.48 µM). The thermogravimetric results demonstrated that both DND and BCNW powders can accelerate thermal degradation. The presence of diamondised nanocarbons, regardless of their type, resulted in a decrease in the decomposition temperature of the composite. The study provides insight into the interactions between composite components and their impact on the electrochemical properties of 3D-printed surfaces, suggesting electroanalytic potential.

Cross-Linking, Morphology, and Physico-Mechanical Properties of GTR/SBS Blends: Dicumyl Peroxide vs. Sulfur System.

In this work, ground tire rubber and styrene-butadiene block copolymer (GTR/SBS) blends at the ratio of 50/50 wt%, with the application of four different SBS copolymer grades (linear and radial) and two types of cross-linking agent (a sulfur-based system and dicumyl peroxide), were prepared by melt compounding. The rheological and cross-linking behavior, physico-mechanical parameters (i.e., tensile properties, abrasion resistance, hardness, swelling degree, and density), thermal stability, and morphology of the prepared materials were characterized. The results showed that the selected SBS copolymers improved the processability of the GTR/SBS blends without any noticeable effects on their cross-linking behavior-which, in turn, was influenced by the type of cross-linking agent used. On the other hand, it was observed that the tensile strength, elongation at break, and abrasion resistance of the GTR/SBS blends cured with the sulfur system (6.1-8.4 MPa, 184-283%, and 235-303 mm3, respectively) were better than those cross-linked by dicumyl peroxide (4.0-7.8 MPa, 80-165%, and 351-414 mm3, respectively). Furthermore, it was found that the SBS copolymers improved the thermal stability of GTR, while the increasing viscosity of the used SBS copolymer also enhanced the interfacial adhesion between the GTR and SBS copolymers, as confirmed by microstructure evaluation.

Processing, Mechanical and Morphological Properties of GTR Modified by SBS Copolymers.

In this work, ground tire rubber (GTR) was thermo-mechanically treated in the presence of styrene-butadiene-styrene (SBS) copolymers. During preliminary investigation, the effects of different SBS copolymer grades, the variable content of SBS copolymer on the Mooney viscosity, and the thermal and mechanical properties of modified GTR were determined. Subsequently, GTR modified by SBS copolymer and cross-linking agents (sulfur-based system and dicumyl peroxide) was characterized by assessment of rheological, physico-mechanical, and morphological properties. Rheological investigations showed that linear SBS copolymer, with the highest melt flow rate among studied SBS grades, was the most promising modifier of GTR, considering processing behavior. It was also observed that an SBS improves the thermal stability of the modified GTR. However, it was found that higher content of SBS copolymer (above 30 wt%) does not bring any effective changes and, for economic reasons, is inefficient. The results showed that samples based on GTR modified by SBS and dicumyl peroxide have better processability and slightly higher mechanical properties compared to samples cross-linked by a sulfur-based system. This is due to the affinity of dicumyl peroxide to the co-cross-linking of GTR and SBS phases.

Multiple Reprocessing of Conductive PLA 3D-Printing Filament: Rheology, Morphology, Thermal and Electrochemical Properties Assessment.

Additive manufacturing technologies are gaining more and more attention, resulting in the development or modification of 3D printing techniques and dedicated materials. On the other hand, economic and ecological aspects force the industry to develop material recycling strategies. In this work, the multiple reprocessing of a commercially available PLA conductive composite with carbon black filler, dedicated to 3D printing, was investigated. The effects of extrusion temperature (190 °C and 200 °C) and reprocessing steps (1-5 steps) on the rheology, morphology, thermal and electrochemical properties of the conductive PLA 3D-printing filament were evaluated. The results showed deterioration of the thermal stability and material strength, as well as the influence of reprocessing on the melting point, which increases after initial melting. The electronic conduction mechanism of the composite depends on the percolation paths and it is also affected by the multiple processing. The reversibility of the [Fe(CN)6]3-/4- redox process diminishes with a higher degradation level of the conductive PLA. Importantly, the material fluidity was too high after the multiple reprocessing, which should be considered and suitably corrected during CB-PLA application as a 3D-printed electrode material.

GTR/Thermoplastics Blends: How Do Interfacial Interactions Govern Processing and Physico-Mechanical Properties?

In this work, GTR/thermoplastics blends (in ratio 50/50 and 75/25 wt.%) were prepared by melt-compounding in an internal mixer. During research, trans-polyoctenamer rubber (TOR), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (EOC), and linear low-density polyethylene (LLDPE), were used in their thermoplastic phase. Microstructure and processing-performance property interrelationships of the studied materials were investigated by: atomic force microscopy (AFM), scanning electron microscopy (SEM), rubber process analyzer (RPA), Mooney viscometer, plastometer, gas chromatography with mass spectrometry, differential scanning calorimetry (DSC), tensile tests and swelling behavior. In blends of thermoplastics with a high content of GTR (50 and 75 wt.%), the thermoplastic modifier type had a significant impact on the processing behavior and microstructure of blends. In terms of the physico-mechanical properties, the GTR/thermoplastics ratio affected elongation at break, hardness, and density, while its effect on tensile strength was negligible. DSC analysis showed that thermoplastics, as modifiers of GTR, should be considered as binders and not plasticizers, as reflected in the almost constant glass-transition temperature of the blends. RPA measurements indicated higher values of G* and η* for GTR-rich blends. SEM showed a rubber-like interfacial break, while AFM confirmed interfacial contact between GTR and thermoplastics.