Interfacial interactions of doped-Ti3C2 MXene/MAPbI3 heterostructures: surfaces and the theoretical approach.

The work function (WF) of perovskite materials is essential for developing optoelectronic devices enabling efficient charge transfer at their interfaces. Perovskite's WF can be tuned by MXenes, a new class of two-dimensional (2D) early transition metal carbides, nitrides, and carbonitrides. Their variable surface terminations or the possibility of introducing elemental dopants could advance perovskites. However, the influence of doped-MXenes on perovskite materials is still not fully understood and elaborated. This study provides mechanistic insight into verifying the tunability of MAPbI3 WF by hybridizing with fluorine-terminated Ti3C2Tx (F-MXene) and nitrogen-doped Ti3C2Tx (N-MXene). We first reveal the interfacial interaction between MAPbI3 and MXenes via X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and photoluminescence spectroscopy (PL). UPS supported by density functional theory (DFT) calculations allowed the description of the influence of F and N on MXene's WF. Furthermore, we developed MAPbI3/MXene heterostructures using F- and N-MXenes. The F-MXenes extended the most WF of MAPbI3 from 4.50 eV up to 3.00 eV, compared to only a small shift for N-MXene. The underlying mechanism was charge transfer from low WF F-MXene to MAPbI3, as demonstrated by PL quenching in MAPbI3/F-MXene heterostructures. Altogether, this work showcases the potential of fluorine-doped MXenes over nitrogen-doped MXenes in advancing perovskite heterostructures, thus opening a door for efficient optoelectronic devices.

Mechanical Properties of Silicon Carbide Composites Reinforced with Reduced Graphene Oxide.

This article presents research on the influence of reduced graphene oxide on the mechanical properties of silicon carbide matrix composites sintered with the use of the Spark Plasma Sintering method. The produced sinters were subjected to a three-point bending test. An increase in flexural strength was observed, which reaches a maximum value of 503.8 MPa for SiC-2 wt.% rGO composite in comparison to 323 MPa for the reference SiC sample. The hardness of composites decreases with the increase in rGO content down to 1475 HV10, which is correlated with density results. Measured fracture toughness values are burdened with a high standard deviation due to the presence of rGO agglomerates. The KIC reaches values in the range of 3.22-3.82 MPa*m1/2. Three main mechanisms responsible for the increase in the fracture toughness of composites were identified: bridging, deflecting, and branching of cracks. Obtained results show that reduced graphene oxide can be used as a reinforcing phase to the SiC matrix, with an especially visible impact on flexural strength.

Effect of Anisotropy of Reduced Graphene Oxide on Thermal and Electrical Properties in Silicon Carbide Matrix Composites.

Reduced graphene oxide, due to its structure, exhibits anisotropic properties, which are particularly evident in electrical and thermal conductivity. This study focuses on examining the influence of reduced graphene oxide in silicon carbide on these properties in directions perpendicular and parallel to the direction of the aligned rGO flakes in produced composites. Reduced graphene oxide is characterized by very high in-plane thermal and electrical conductivity. It was observed that the addition of rGO increases thermal conductivity from 64 W/mK (reference sample) up to 98 W/mK for a SiC-3 wt.% rGO composite in the direction parallel to the rGO flakes. In the perpendicular direction, the values were slightly lower, reaching up to 84 W/mK. The difference observed in electrical conductivity values is more significant and is 1-2 orders of magnitude higher for the flakes' alignment direction. The measured electrical conductivity increased from 1.2710-8 S/m for the reference SiC sinter up to 1.55 × 10-5 S/m and 1.2410-4 S/m for the composites with 3 wt.% rGO for the perpendicular and parallel directions, respectively. This represents an enhancement of four orders of magnitude, with a clearly visible influence of the anisotropy of the rGO. The composite's enhanced electrical and thermal conductivity make it particularly attractive for electronic devices and high-power applications.

Engineering the surface of Nbn+1CnTx MXenes to versatile bio-activity towards microorganisms.

Two-dimensional (2D) transition metal carbides/nitrides (MXenes) are potential antibacterial agents. However, their activity against microorganisms is not fully understood. It could relate to MXenes' surface which further influences their biocidal action. Herein, we report no continuous biocidal activity for delaminated 2D niobium-based MXenes (Nbn+1XnTx) such as Nb2CTx and Nb4C3Tx prepared with HF/TMAOH protocol. Biocidal activity towards Bacillus subtilis and Staphylococcus aureus microorganisms was achieved by surface-functionalization with lysozyme macromolecule. MXenes' engineering with lysozyme changed MXene's surface charge from negative into positive thus enabling the elimination of bacteria cells during 48 h of incubation. In contrast, Nb4C3Tx functionalized with collagen stimulated the growth of Bacillus subtilis by 225 %, showing MXene's biocompatibility towards this particular strain. Altogether, our results show that MXenes are incredibly bio-tunable. Opposing bio-effects such as antimicrobial or growth-stimulating can be achieved towards various microorganisms with rational surface engineering.

Influence of Low Temperature Plasma Oxidizing on the Bioactivity of NiTi Shape Memory Alloy for Medical Applications.

The present study elucidates the impact of glow discharge oxidation within a low-temperature plasma environment on the bioactivity characteristics of an NiTi shape memory alloy. The properties of the produced surface layers, such as structure (TEM observations), surface morphology (SEM observations), chemical and phase composition (EDS and XRD measurements), wettability (optical gonimeter), and the biological response of osteoblasts and platelets to the oxidized surface compared with the NiTi alloy without a surface layer are presented. The presented surface modification of the NiTi shape memory alloy, achieved through oxidizing in a low-temperature plasma environment, led to the creation of a continuous surface layer composed of nanocrystalline titanium oxide TiO2 (rutile). The findings obtained from this study provide evidence that the oxidized layer augments the bioactivity of the shape memory alloy. This augmentation was substantiated through the spontaneous biomimetic deposition of apatite from a simulated body fluid (SBF) solution. Furthermore, the modified surface exhibited improved osteoblast proliferation, and enhanced platelet adhesion and activation. This proposed surface modification strategy holds promise as a prospective solution to enhance the biocompatibility and bioactivity of NiTi shape memory alloy intended for prolonged use in bone implant applications.

Synthesis of Ti3SiC2 Phases and Consolidation of MAX/SiC Composites-Microstructure and Mechanical Properties.

The article describes the Ti3SiC2 powder synthesis process. The influence of the molar ratio and two forms of carbon on the phase composition of the obtained powders was investigated. The synthesis was carried out using a spark plasma sintering (SPS) furnace. In addition, using the obtained powders, composites reinforced with SiC particles were produced. The obtained results showed no effect of the carbon form and a significant impact of annealing on the purity of the powders after synthesis. The composites were also consolidated using an SPS furnace at two temperatures of 1300 and 1400 °C. The tests showed low density and hardness for sinters from 1300 °C (maximum 3.97 g/cm3 and 447 HV5, respectively, for composite reinforced with 10% SiC). These parameters significantly increase for composites sintered at 1400 °C (maximum density 4.43 g/cm3 and hardness 1153 HV5, for Ti3AlC2-10% SiC). In addition, the crack propagation analysis showed mechanisms typical for granular materials and laminates.

Photocatalytic Activity of the Oxidation Stabilized Ti3 C2 Tx MXene in Decomposing Methylene Blue, Bromocresol Green and Commercial Textile Dye.

Two-dimensional MXenes are excellent photocatalysts. However, their low oxidation stability makes controlling photocatalytic processes challenging. For the first time, this work elucidates the influence of the oxidation stabilization of model 2D Ti3 C2 Tx MXene on its optical and photocatalytic properties. The delaminated MXene is synthesized via two well-established approaches: hydrofluoric acid/tetramethylammonium hydroxide (TMAOH-MXene) and minimum intensive layer delamination with hydrochloric acid/lithium fluoride (MILD-MXene) and then stabilized by L-ascorbic acid. Both MXenes at a minimal concentration of 32 mg L-1 show almost 100% effectiveness in the 180-min photocatalytic decomposition of 25 mg L-1 model methylene blue and bromocresol green dyes. Industrial viability is achieved by decomposing a commercial textile dye having 100 times higher concentration than that of model dyes. In such conditions, MILD-MXene is the most efficient due to less wide optical band gap than TMAOH-MXene. The MILD-MXene required only few seconds of UV light, simulated white light, or 500 nm (cyan) light irradiation to fully decompose the dye. The photocatalytic mechanism of action is associated with the interplay between surface dye adsorption and the reactive oxygen species generated by MXene under light irradiation. Importantly, both MXenes are successfully reused and retained approximately 70% of their activity.

Ambient Processed rGO/Ti3CNTx MXene Thin Film with High Oxidation Stability, Photosensitivity, and Self-Cleaning Potential.

Solution-based processing offers advantages for producing thin films due to scalability, low cost, simplicity, and benignity to the environment. Here, we develop conductive and photoactivated self-cleaning reduced graphene oxide (rGO)/Ti3CNTx MXene thin films via spin coating under ambient conditions. The addition of a thin rGO layer on top of Ti3CNTx resulted in up to 45-fold improvement in the environmental stability of the film compared to the bare Ti3CNTx film. The optimized rGO/Ti3CNTx thin film exhibits an optical transmittance of 74% in the visible region of the spectrum and a sheet resistance of 19 kΩ/sq. The rGO/Ti3CNTx films show high rhodamine B discoloration activity upon light irradiation. Under UV irradiation, the electrically conductive MXene in combination with in situ formed semiconducting titanium oxide induces photogenerated charge carriers, which could potentially be used in photocatalysis. On the other hand, due to film transparency, white light irradiation can bleach the adsorbed dye via photolysis. This study opens the door for using MXene thin films as multifunctional coatings with conductive and potentially self-cleaning properties.

Properties of Cold Sprayed Titanium and Titanium Alloy Coatings after Laser Surface Treatment.

Additive manufacturing (AM) has seen remarkable development in recent years due to relatively high efficiency of the process. Cold spraying (CS) is a particular method of AM, in which titanium and titanium alloy powders are used. CS is a very competitive technology enabling the deposition of coatings, repairing machine parts, and manufacturing new components. For specific applications, the surface of cold-sprayed materials may require further processing. This paper reports an attempt to employ laser surface treatment (LST) of cold-sprayed coatings on an aluminium alloy substrate. The influence of laser beam interaction time on the coatings' properties was analysed. The microstructure was investigated and observed employing scanning electron microscopy (SEM). To evaluate residual stress after CS and LST, the sin2ψ technique was used. Investigations were also performed on Vickers hardness, contact angle, and surface roughness. Significant changes in the surface morphology of the coatings and elevated residual stress levels dependent on the laser beam interaction time were observed. Increased Vickers hardness was recorded for titanium alloy Ti6Al4V. LST also led to increased surface hydrophilicity of the modified materials Ti and Ti6Al4V.

Understanding the mechanism of Nb-MXene bioremediation with green microalgae.

Rapidly developing nanotechnologies and their integration in daily applications may threaten the natural environment. While green methods of decomposing organic pollutants have reached maturity, remediation of inorganic crystalline contaminants is major problem due to their low biotransformation susceptibility and the lack of understanding of material surface-organism interactions. Herein, we have used model inorganic 2D Nb-based MXenes coupled with a facile shape parameters analysis approach to track the mechanism of bioremediating 2D ceramic nanomaterials with green microalgae Raphidocelis subcapitata. We have found that microalgae decomposed the Nb-based MXenes due to surface-related physicochemical interactions. Initially, single and few-layered MXene nanoflakes attached to microalgae surfaces, which slightly reduced algal growth. But with prolonged surface interaction, the microalgae oxidized MXene nanoflakes and further decomposed them into NbO and Nb2O5. Since these oxides were nontoxic to microalgal cells, they consumed Nb-oxide nanoparticles by an uptake mechanism thus enabling further microalgae recovery after 72 h of water treatment. The uptake-associated nutritional effects were also reflected by cells' increased size, smoothed shape and changed growth rates. Based on these findings, we conclude that short- and long-term presence of Nb-based MXenes in freshwater ecosystems might cause only negligible environmental effects. Notably, by using 2D nanomaterials as a model system, we show evidence of the possibility of tracking even fine material shape transformations. In general, this study answers an important fundamental question about the surface interaction-associated processes that drive the mechanism of 2D nanomaterials' bioremediation as well as provides the fundamental basis for further short- and long-term investigations on the environmental effects of inorganic crystalline nanomaterials.

Modelling and Characterisation of Residual Stress of SiC-Ti3C2Tx MXene Composites Sintered via Spark Plasma Sintering Method.

This article presents an attempt to determine the effect of the MXene phase addition and its decomposition during sintering with the use of the spark plasma sintering method on mechanical properties and residual stress of silicon carbide based composites. For this purpose, the unreinforced silicon carbide sinter and the silicon carbide composite with the addition of 2 wt.% of Ti3C2Tx were tested. The results showed a significant increase of fracture toughness and hardness for composite, respectively 36% and 13%. The numerical study involving this novel method of modelling shows the presence of a complex state of stress in the material, which is related to the anisotropic properties of graphitic carbon structures formed during sintering. An attempt to determine the actual values of residual stress in the tested materials using Raman spectroscopy was also made. These tests showed a good correlation with the constructed numerical model and confirmed the presence of a complex state of residual stress.

Influence of Different Types of Cemented Carbide Blades and Coating Thickness on Structure and Properties of TiN/AlTiN and TiAlN/a-C:N Coatings Deposited by PVD Techniques for Machining of Wood-Based Materials.

The influence of different types of cemented carbide blades and thickness of TiAlN/a-C:N and TiN/AlTiN protective coatings used in the wood industry on cutting performance has been studied. Three types of WC-Co cemented carbide blades with different cobalt content were used in the study. The thicknesses of both types of coatings were ~2 and ~5 µm. The structure, chemical and phase composition were studied using transmission and scanning electron microscopy (TEM, SEM), X-ray dispersion spectroscopy (EDX) and X-ray diffraction (XRD), respectively. The adhesion was evaluated by scratch test. Nanohardness and durability tests of uncoated and coated blades were performed. We found that the blades covered with 5 µm TiN/AlTiN coatings exhibited the best durability characteristic. The cutting distances were within the range ~6700-~7080 depending on the substrates in comparison with pure substrates (~4300-~4900) and 2 µm TiN/AlTiN coatings (~5400-~6600). The presence of a thin and soft outer a-C:N layer aggravates the nanohardness and durability of the coated blades.

Influence of Ti3C2Tx MXene and Surface-Modified Ti3C2Tx MXene Addition on Microstructure and Mechanical Properties of Silicon Carbide Composites Sintered via Spark Plasma Sintering Method.

This article presents new findings related to the problem of the introduction of MXene phases into the silicon carbide matrix. The addition of MXene phases, as shown by the latest research, can significantly improve the mechanical properties of silicon carbide, including fracture toughness. Low fracture toughness is one of the main disadvantages that significantly limit its use. As a part of the experiment, two series of composites were produced with the addition of 2D-Ti3C2Tx MXene and 2D-Ti3C2Tx surface-modified MXene with the use of the sol-gel method with a mixture of Y2O3/Al2O3 oxides. The composites were obtained with the powder metallurgy technique and sintered with the Spark Plasma Sintering method at 1900 °C. The effect adding MXene phases had on the mechanical properties and microstructure of the produced sinters was investigated. Moreover, the influence of the performed surface modification on changes in the properties of the produced composites was determined. The analysis of the obtained results showed that during sintering, the MXene phases oxidize with the formation of carbon flakes playing the role of reinforcement. The influence of the Y2O3/Al2O3 layer on the structure of carbon flakes and the higher quality of the interface was also demonstrated. This was reflected in the higher mechanical properties of composites with the addition of modified Ti3C2Tx. Composites with 1 wt.% addition of Ti3C2Tx M are characterized with a fracture toughness of 5 MPa × m0.5, which is over 50% higher than in the case of the reference sample and over 15% higher than for the composite with 2.5 wt.% addition of Ti3C2Tx, which showed the highest fracture toughness in this series.

Molding Binder Influence on the Porosity and Gas Permeability of Ceramic Casting Molds.

The investment casting process is widely used in the aerospace industry to produce complex engine parts. The article determines the properties of quartz powders, nanosilica dioxide binders, and multilayer samples of ceramic casting molds. The properties of spherical molds obtained using an alcohol-water system derived from hydrolyzed ethyl silicate (ZKE) and LUDOX PX-30 (type Q1) were compared with those obtained in water systems derived from Remasol Plus and Remasol Premium binders (type Q2). The spherical samples are composed of seven layers made with the use of an immersion-sprinkling method. To assess the properties of the molds, X-ray microscopy (µCT), scanning electron microscopy (SEM), and gas permeability analysis over a temperature range of 20-950 °C were utilized. The binder type is proven to affect the properties of the casting mold samples. The material obtained in the water system, Q2, has advantageous properties such as a high porosity and gas permeability.

Influence of MXene (Ti3C2) Phase Addition on the Microstructure and Mechanical Properties of Silicon Nitride Ceramics.

This paper discusses the influence of Ti3C2 (MXene) addition on silicon nitride and its impact on the microstructure and mechanical properties of the latter. Composites were prepared through powder processing and sintered using the spark plasma sintering (SPS) technic. Relative density, hardness and fracture toughness, were analyzed. The highest fracture toughness at 5.3 MPa·m1/2 and the highest hardness at HV5 2217 were achieved for 0.7 and 2 wt.% Ti3C2, respectively. Moreover, the formation of the Si2N2O phase was observed as a result of both the MXene addition and the preservation of the α-Si3N4→ß-Si3N4 phase transformation during the sintering process.