Pokročilé polymerní materiály a kompozit

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Anatase and rutile nanoparticles in photopolymer 3D-printed nanocomposites: Band gap-controlled electron interactions in free-radical and cationic photocuring
(Elsevier, 2024-07-01) Korčušková, Martina; Svatík, Juraj; Tomal, Wiktoria; Šikyňová, Aneta; Vishakha, Vishakha; Petko, Filip; Galek, Mariusz; Stalmach, Paweł; Ortyl, Joanna; Lepcio, Petr
The preparation of functional photopolymer nanocomposites is affected by both the physical and chemical interactions of nanoparticles (NPs) and polymer resin. Some NPs, such as semiconducting metal oxides, may contribute by their photocatalytic behavior and electron transfer, influencing the kinetics of the photopolymerization reaction. This study has investigated the complex effect of titanium dioxide (TiO 2 ) NPs in anatase and rutile form on the conversion, kinetics, and printability of free -radical and cationic photopolymerization resin. Two different polymorphs of TiO 2 NPs ensured identical chemical properties, but different physical effects related to their varying band gap energies and electron transfer efficiency. These parameters were found to be crucial for influencing the photopolymerization kinetics. While rutile showed a more pronounced enhancement of the free -radical photopolymerization ' s conversion and kinetics, cationic photopolymerization was favourably affected only by anatase NPs due to the photosensitization effect. These findings are critical in understanding and designing functional nanocomposite materials processed by vat photopolymerization 3D printing that could find use in optical, medical, or environmental applications.
Graphene quantum dots-From spectroscopic performance to 3D printing applications and interaction studies with normal and cancer cells
(Elsevier, 2024-05-27) Krok-Janiszewska, Dominika; Wielgus, Weronika; Środa, Patrycja; Tyszka-Czochara, Małgorzata; Lepcio, Petr; Kasprzyk, Wiktor; Ortyl, Joanna
In this study, different types of graphene quantum dots (GQDs) are investigated to understand their spectroscopic properties. Morphological and size analyses were performed. The mechanism of action of radical photopolymerization was evaluated. The obtained materials proved to be useful for developing efficient photoinitiating systems for 3D printing applications. In addition, the cytotoxicity of the GQDs was studied, and their effects on living cells were investigated. We demonstrated that GQDs can not only act as efficient photoinitiators but also as constituents of hydrogels that express very low toxicity and may interact with cells. The latter makes it possible to study them in the future as useful modern biosensors.
Biaxial porosity gradient and cell size adjustment improve energy absorption in rigid and flexible 3D-printed reentrant honeycomb auxetic structures
(Elsevier, 2024-06-01) Štaffová, Martina; Ondreáš, František; Žídek, Jan; Jančář, Josef; Lepcio, Petr
This paper compares different uniaxial and biaxial graded designs of auxetic reentrant honeycomb structures to enhance their mechanical properties, especially the specific energy absorption under compressive load. The lattice structures were 3D printed using the vat photopolymerization masked-stereolithography technique from two different materials - tough (OR) and flexible (FR). The results were evaluated from a material and structural point of view, investigating the effect of porosity, cell number, size, graded design, and fracture mode. The universally best energy-absorbing performance was found in a biaxially graded structure with a center-wise location of the highest local porosity. Depending on the used resin, its energy absorption capacity was up to 2-3 times enhanced compared to a reference uniform-porosity auxetic design. The presented data constitutes a fundamental understanding of auxetic structures and identifies practical approaches for tuning the auxetic structures' performance regarding their mechanical response. Finally, this study demonstrates the potential of shape versatility offered by 3D printing and other additive manufacturing techniques.
Antidurotaxis Droplet Motion onto Gradient Brush Substrates
(American Chemical Society, 2023-09-06) Kajouri, Russell; Theodorakis, Panagiotis E.; Žídek, Jan; Milchev, Andrey
Durotaxis motion is a spectacular phenomenon manifesting itself by the autonomous motion of a nano-object between parts of a substrate with different stiffness. This motion usually takes place along a stiffness gradient from softer to stiffer parts of the substrate. Here, we propose a new design of a polymer brush substrate that demonstrates antidurotaxis droplet motion, that is, droplet motion from stiffer to softer parts of the substrate. By carrying out extensive molecular dynamics simulation of a coarse-grained model, we find that antidurotaxis is solely controlled by the gradient in the grafting density of the brush and is favorable for fluids with a strong attraction to the substrate (low surface energy). The driving force of the antidurotaxial motion is the minimization of the droplet-substrate interfacial energy, which is attributed to the penetration of the droplet into the brush. Thus, we anticipate that the proposed substrate design offers a new understanding and possibilities in the area of autonomous motion of droplets for applications in microfluidics, energy conservation, and biology.
Matching Low Viscosity with Enhanced Conductivity in Vat Photopolymerization 3D Printing: Disparity in the Electric and Rheological Percolation Thresholds of Carbon-Based Nanofillers Is Controlled by the Matrix Type and Filler Dispersion
(AMER CHEMICAL SOC, 2023-11-25) Sevriugina, Veronika; Pavliňák, David; Ondreáš, František; Jašek, Ondřej; Štaffová, Martina; Lepcio, Petr
This study investigated the impact of carbonaceous fillers (carbon black, multiwalled carbon nanotubes, graphene, and highly defective graphene) on aromatic and nonaromatic photopolymer resins' properties, such as viscosity, long-term stability, complex permittivity, curing efficiency, final conversion, storage modulus, heat deflection and glass transition temperatures, network density, and DC resistivity. The presented results also highlight challenges that must be addressed in designing and processing carbonaceous filler-based 3D-printed photopolymer resins. The improved dielectric and electrical properties were closely tied to the dispersion quality and filler-matrix affinity. It favored the enhanced dispersion of anisotropic fillers (nanotubes) in a compatible matrix above their percolation threshold. On the other hand, the dispersed filler worsens printability due to the elevated viscosity and deteriorated penetration depth. Nonetheless, electrical and rheological percolation was found at different filler concentrations. This window of despaired percolation combines highly enhanced conductivity with only mildly increased viscosity and good printability.

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