Superhydrophobic SLA 3D printed materials modified with nanoparticles biomimicking the hierarchical structure of a rice leaf.

The rice leaf, combining the surface properties of lotus leaves and shark skin, presents outstanding superhydrophobic properties motivating its biomimesis. We created a novel biomimetic rice-leaf superhydrophobic surface by a three-level hierarchical structure, using for a first time stereolithographic (SLA) 3D printed channels (100µm width) with an intrinsic roughness from the printing filaments (10µm), and coated with TiO2 nanoparticles (22 and 100nm). This structure presents a maximum advancing contact angle of 165° characterized by lower both anisotropy and hysteresis contact angles than other 3D printed surfaces, due to the presence of air pockets at the surface/water interface (Cassie-Baxter state). Dynamic water-drop tests show that the biomimetic surface presents self-cleaning, which is reduced under UV-A irradiation. The biomimetic surface further renders an increased floatability to 3D printed objects meaning a drag-reduction due to reduced water/solid contact area. Numerical simulations of a channel with a biomimetic wall confirm that the presence of air is essential to understand our results since it increases the average velocity and decreases the friction factor due to the presence of a wall-slip velocity. Our findings show that SLA 3D printing is an appropriate approach to develop biomimetic superhydrophobic surfaces for future applications in anti-fouling and drag-reduction devices.

Nickel Nanopillar Arrays Electrodeposited on Silicon Substrates Using Porous Alumina Templates.

Nickel nanopillar arrays were electrodeposited onto silicon substrates using porous alumina membranes as a template. The characterization of the samples was done by scanning electron microscopy, X-ray diffraction, and alternating force gradient magnetometry. Ni nanostructures were directly grown on Si by galvanostatic and potentiostatic electrodeposition techniques in three remarkable charge transfer configurations. Differences in the growth mechanisms of the nanopillars were observed, depending on the deposition method. A high correlation between the height of the nanopillars and the charge synthesis was observed irrespective of the electrochemical technique. The magnetization measurements demonstrated a main dependence with the height of the nanopillars. The synthesis of Ni nanosystems with a controllable aspect ratio provides an effective way to produce well-ordered networks for wide scientific applications.

New Deformation-Induced Nanostructure in Silicon.

Nanostructures in silicon (Si) induced by phase transformations have been investigated during the past 50 years. Performances of nanostructures are improved compared to that of bulk counterparts. Nevertheless, the confinement and loading conditions are insufficient to machine and fabricate high-performance devices. As a consequence, nanostructures fabricated by nanoscale deformation at loading speeds of m/s have not been demonstrated yet. In this study, grinding or scratching at a speed of 40.2 m/s was performed on a custom-made setup by an especially designed diamond tip (calculated stress under the diamond tip in the order of 5.11 GPa). This leads to a novel approach for the fabrication of nanostructures by nanoscale deformation at loading speeds of m/s. A new deformation-induced nanostructure was observed by transmission electron microscopy (TEM), consisting of an amorphous phase, a new tetragonal phase, slip bands, twinning superlattices, and a single crystal. The formation mechanism of the new phase was elucidated by ab initio simulations at shear stress of about 2.16 GPa. This approach opens a new route for the fabrication of nanostructures by nanoscale deformation at speeds of m/s. Our findings provide new insights for potential applications in transistors, integrated circuits, diodes, solar cells, and energy storage systems.

Covalent organic frameworks in tribology - A perspective.

Two-dimensional covalent organic frameworks (2D COFs) are an emerging class of crystalline porous materials formed through covalent bonds between organic building blocks. COFs uniquely combine a large surface area, an excellent stability, numerous abundant active sites, and tunable functionalities, thus making them highly attractive for numerous applications. Especially, their abundant active sites and weak interlayer interaction make these materials promising candidates for tribological research. Recently, notable attention has been paid to COFs as lubricant additives due to their excellent tribological performance. Our review aims at critically summarizing the state-of-art developments of 2D COFs in tribology. We discuss their structural and functional design principles, as well as synthetic strategies with a special focus on tribology. The generation of COF thin films is also assessed in detail, which can alleviate their most challenging drawbacks for this application. Subsequently, we analyze the existing state-of-the-art regarding the usage of COFs as lubricant additives, self-lubrication composite coatings, and solid lubricants at the nanoscale. Finally, critical challenges and future trends of 2D COFs in tribology are outlined to initiate and boost new research activities in this exciting field.

Introduction to 2D materials and their applications.

Diana Berman, Agnieszka Jastrzebska, Massimiliano Papi, and Andreas Rosenkranz introduce the RSC Advances themed issue on 2D materials and their applications.

Tribology of 2D black phosphorus - Current state-of-the-art and future potential.

Since the first mechanical exfoliation of graphene in 2004, the interest in 2D materials has significantly risen due to their outstanding property combination. Multiple 2D materials have been synthesized until today, while black phosphorus (BP) resembles one of their latest additions. The unique properties of BP, especially for electronic and optical devices (i.e., high carrier mobility and electrical conduction, field-effect transistor, layer-dependent bandgap, anisotropic transport), have gained notable attention. However, its layered structure, similar to those of graphene and MoS2, is also advantageous to optimize the friction and wear performance. Moreover, the strong in-plane covalent bonds and weak interlayer van-der-Waals forces favour the formation of low-friction and wear-resistant films. Although BP holds a great tribological potential, the literature to date on this topic is rather scarce. Therefore, it is a timely moment to holistically summarize the synthesis approaches and properties of BP thus guiding interested researchers to use it in mechanical/tribological applications. The existing state-of-the-art regarding tribological research is critically discussed and compared to other 2D materials thus highlighting existing research gaps and paving the way for future research activities.

2D materials for Tribo-corrosion and -oxidation protection: A review.

The recent rise of 2D materials has extended the opportunities of tuning a variety of properties. Tribo-corrosion, the complex synergy between mechanical wear and chemical corrosion, poses significant challenges across numerous industries where materials are subjected to both tribological stressing and corrosive environments. This intricate interplay often leads to accelerated material degradation and failure. This review critically assesses the current state of utilizing 2D nanomaterials to enhance tribo-corrosion and -oxidation behavior. The paper summarizes the fundamental knowledge about tribo-corrosion and -oxidation mechanisms before assessing the key contributions of 2D materials, including graphene, transition metal chalcogenides, hexagonal boron nitride, MXenes, and black phosphorous, regarding the resulting friction and wear behavior. The protective roles of these nanomaterials against corrosion and oxidation are investigated, highlighting their potential in mitigating material degradation. Furthermore, we delve into the nuanced interplay between mechanical and corrosive factors in the specific application of 2D materials for tribo-corrosion and -oxidation protection. The synthesis of key findings underscores the advancements achieved through integrating 2D nanomaterials. An outlook for future research directions is provided, identifying unexplored avenues, and proposing strategies to propel the field forward. This analysis aims at guiding future investigations and developments at the dynamic intersection of 2D nanomaterials, tribo-corrosion, and -oxidation protection.

MXene-Based Elastomer Mimetic Stretchable Sensors: Design, Properties, and Applications.

Flexible sensors based on MXene-polymer composites are highly prospective for next-generation wearable electronics used in human-machine interfaces. One of the motivating factors behind the progress of flexible sensors is the steady arrival of new conductive materials. MXenes, a new family of 2D nanomaterials, have been drawing attention since the last decade due to their high electronic conductivity, processability, mechanical robustness and chemical tunability. In this review, we encompass the fabrication of MXene-based polymeric nanocomposites, their structure-property relationship, and applications in the flexible sensor domain. Moreover, our discussion is not only limited to sensor design, their mechanism, and various modes of sensing platform, but also their future perspective and market throughout the world. With our article, we intend to fortify the bond between flexible matrices and MXenes thus promoting the swift advancement of flexible MXene-sensors for wearable technologies.

Effect of vacancies and edges in promoting water chemisorption on titanium-based MXenes.

The functionality of two-dimensional (2D) transition metal carbides and nitrides (MXenes) in technological applications greatly depends on their wettability. For instance, MXenes' layer stability against degradative oxidation is notably reduced when stored in aqueous solutions, leading to the transformation into oxides. In this work, we study water adsorption on Ti-based MXenes by ab initio calculations. The energy gains for the molecular adsorption on Tin+1XnT2 is evaluated as a function of the termination (T = F, O, OH, mixture), the carbon/nitrogen ratio (X = C, N), the layer thickness (n) and water coverage. MXenes' hydrophilicity tends to increase due to the presence of defects as vacancies and flake edges. We demonstrate that physical adsorption occurs through hydrogen bonding on both defect-free layers and layers containing C/N or Ti atomic vacancies, with -OH terminations providing the strongest interactions (0.40-0.65 eV). In contrast, strong water chemisorption is observed on surfaces with a single termination vacancy (0.60-1.20 eV), edges (0.75-0.85 eV), and clusters of defects (1.00-1.80 eV). We verified that the presence of undercoordinated Ti atoms on the surface is the key factor in promoting H2O chemisorption, i.e., the degradative oxidation.

Perspectives of 2D MXene Tribology.

The large and rapidly growing family of 2D early transition metal carbides, nitrides, and carbonitrides (MXenes) raises significant interest in the materials science and chemistry of materials communities. Discovered a little more than a decade ago, MXenes have already demonstrated outstanding potential in various applications ranging from energy storage to biology and medicine. The past two years have witnessed increased experimental and theoretical efforts toward studying MXenes' mechanical and tribological properties when used as lubricant additives, reinforcement phases in composites, or solid lubricant coatings. Although research on the understanding of the friction and wear performance of MXenes under dry and lubricated conditions is still in its early stages, it has experienced rapid growth due to the excellent mechanical properties and chemical reactivities offered by MXenes that make them adaptable to being combined with other materials, thus boosting their tribological performance. In this perspective, the most promising results in the area of MXene tribology are summarized, future important problems to be pursued further are outlined, and methodological recommendations that could be useful for experts as well as newcomers to MXenes research, in particular, to the emerging area of MXene tribology, are provided.

Optically Active MXenes in Van der Waals Heterostructures.

The vertical integration of distinct 2D materials in van der Waals (vdW) heterostructures provides the opportunity for interface engineering and modulation of electronic as well as optical properties. However, scarce experimental studies reveal many challenges for vdW heterostructures, hampering the fine-tuning of their electronic and optical functionalities. Optically active MXenes, the most recent member of the 2D family, with excellent hydrophilicity, rich surface chemistry, and intriguing optical properties, are a novel 2D platform for optoelectronics applications. Coupling MXenes with various 2D materials into vdW heterostructures can open new avenues for the exploration of physical phenomena of novel quantum-confined nanostructures and devices. Therefore, the fundamental basis and recent findings in vertical vdW heterostructures composed of MXenes as a primary component and other 2D materials as secondary components are examined. Their robust designs and synthesis approaches that can push the boundaries of light-harvesting, transition, and utilization are discussed, since MXenes provide a unique playground for pursuing an extraordinary optical response or unusual light conversion features/functionalities. The recent findings are finally summarized, and a perspective for the future development of next-generation vdW multifunctional materials enriched by MXenes is provided.

Additively manufactured MAX- and MXene-composite scaffolds for bone regeneration- recent advances and future perspectives.

Human bones can suffer from various injuries, such as fractures, bone cancer, among others, which has initiated research activities towards bone replacement using advanced bio-materials. However, it is still challenging to design bio-scaffolds with bone-inducing agents to regenerate bone defects. In this regard, MAX-phases and MXenes (early transition metal carbides and/or nitrides) have gained notable attention due to their unique hydrophilicity, bio-compatibility, chemical stability, and photothermal properties. They can be used in bone tissue engineering as a suitable replacement or reinforcement for common bio-materials (polymers, bio-glasses, metals, or hydroxyapatite). To fabricate bio-scaffolds, additive manufacturing is prospective due to the possibility of controlling porosity and creating complex shapes with high resolution. Until now, no comprehensive article summarizing the existing state-of-the-art related to bone scaffolds reinforced by MAX-phases and MXenes fabricated by additive manufacturing has been published. Therefore, our article addresses the reasons for using bone scaffolds and the importance of choosing the most suitable material. We critically discuss the recent developments in bone tissue engineering and regenerative medicine using MAX-phases and MXenes with a particular emphasis on manufacturing, mechanical properties, and bio-compatibility. Finally, we discuss the existing challenges and bottlenecks of bio-scaffolds reinforced by MAX-phases and MXenes before deriving their future potential.

Macroscale Superlubricity Induced by MXene/MoS2 Nanocomposites on Rough Steel Surfaces under High Contact Stresses.

Toward the goal of achieving superlubricity, or near-zero friction, in industrially relevant material systems, solution-processed multilayer Ti3C2Tx-MoS2 blends are spray-coated onto rough 52100-grade steel surfaces as a solid lubricant. The tribological performance was assessed in a ball-on-disk configuration in a unidirectional sliding mode. The test results indicate that Ti3C2Tx-MoS2 nanocomposites led to superlubricious states, which has hitherto been unreported for both individual pristine materials, MoS2 and Ti3C2Tx, under macroscale sliding conditions, indicating a synergistic mechanism enabling the superlative performance. The processing, structure, and property correlation were studied to understand the underlying phenomena. Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy revealed the formation of an in situ robust tribolayer that was responsible for the performance at high contact pressures (>1.1 GPa) and sliding speeds (0.1 m/s). This report presents the lowest friction obtained by either MoS2 or MXene or any combination of the two so far.

Unveiling the tribological potential of MXenes-current understanding and future perspectives.

Reducing energy consumption and CO2 emissions by improving the tribological performance of mechanical systems relies on the development of new lubrication concepts. Two-dimensional (2D) materials have been the subject of extensive tribological research due to their unique physical and chemical properties. 2D transition metal carbides, nitrides, and carbonitrides (MXenes), with their tuneable chemistry and structure, are a relatively new addition to the family of 2D materials. MXenes' good strength and stiffness, easy-to-shear ability, capability to form wear-resistant tribofilms, and the possibility to control their surface chemistry make them appealing candidates to be explored for tribological purposes. This review provides a comprehensive overview of MXenes' tribology, covering their structure-property relationship, synthesis approaches, deposition methods to generate MXene coatings for tribological purposes, and their fundamental tribological mechanisms. Furthermore, detailed insights into studies exploring MXenes' tribological performance from the nano- to the macro-scale are presented with special emphasis on their use as self-lubricating solid lubricants, lubricant additives, and reinforcement phases in composites.

Layer-Dependent Nanowear of Graphene Oxide.

The mechanical performance and surface friction of graphene oxide (GO) were found to inversely depend on the number of layers. Here, we demonstrate the non-monotonic layer-dependence of the nanowear resistance of GO nanosheets deposited on a native silicon oxide substrate. As the thickness of GO increases from ∼0.9 nm to ∼14.5 nm, the nanowear resistance initially demonstrated a decreasing and then an increasing tendency with a critical number of layers of 4 (∼3.6 nm in thickness). This experimental tendency corresponds to a change of the underlying wear mode from the overall removal to progressive layer-by-layer removal. The phenomenon of overall removal disappeared as GO was deposited on an H-DLC substrate with a low surface energy, while the nanowear resistance of thicker GO layers was always higher. Combined with density functional theory calculations, the wear resistance of few-layer GO was found to correlate with the substrate's surface energy. This can be traced back to substrate-dependent adhesive strengths of GO, which correlated with the GO thickness originating from differences in the interfacial charge transfer. Our study proposes a strategy to improve the antiwear properties of 2D layered materials by tuning their own thickness and/or the interfacial interaction with the underlying substrate.

Covalent functionalization of MXenes for tribological purposes - a critical review.

Transition metal carbides, nitrides and carbonitrides (MXenes) have recently attracted notable attention in tribology and, particularly solid lubrication, due to their low shear strength and ability to form low-friction, wear-resistant tribo-layers. Their use as lubricant additives has only shown limited success due to their inherent hydrophilic character, causing a low phase-compatibility and dispersion-stability with pure base oils. To overcome this shortcoming and to boost MXenes' tribological performance as lubricant additive and reinforcement phase in composites, their tuneable surface chemistry moves into the focus of current research. Originating from chemical etching to synthesize MXenes, their outer surface contains a variety of surface terminations, which can function as anchoring points for molecules via covalent grafting/functionalization. By adopting an adequate functionalization strategy, this, in turn, can help to tailor MXenes' hydrophobicity, dispersion stability, restacking tendency, or oxidation resistance. This directly affects their dispersion stability in base oils and improves their phase compatibility with other matrix materials in composites, thus resulting in an enhanced tribological performance. Therefore, this review concisely summarizes the existing state-of-the-art regarding MXenes' covalent functionalization with a particular emphasis on tribological properties and needs, a topic, which has not been holistically reviewed yet. The first chapter sheds light on the existing synthesis approaches with detailed insights regarding the resulting surface terminations, which are crucial for the subsequent chemical functionalization. After summarizing strategies to increase their interlayer distance to improve the accessibility for chemical functionalization and the existing state-of-the art regarding MXene tribology, we critically discuss the existing functionalization strategies using different coupling agents (organosilanes, organophosphorus agents, aryldiazonium agents, among others). Subsequently, we emphasize on the crucial role of homogeneously distributed -OH surface terminations to guarantee the overall success of the functionalization approach and to boost the resulting tribological performance. Lastly, we address the existing challenges and derive future research directions. We anticipate that our article can serve as an excellent guide for MXenes' chemical functionalization, which can be useful in various applications including tribology thus paving the way towards enhanced physical and chemical properties of MXenes.

Nanoscale MXene Interlayer and Substrate Adhesion for Lubrication: A Density Functional Theory Study.

Understanding the interlayer interaction at the nanoscale in two-dimensional (2D) transition metal carbides and nitrides (MXenes) is important to improve their exfoliation/delamination process and application in (nano)-tribology. The layer-substrate interaction is also essential in (nano)-tribology as effective solid lubricants should be resistant against peeling-off during rubbing. Previous computational studies considered MXenes' interlayer coupling with oversimplified, homogeneous terminations while neglecting the interaction with underlying substrates. In our study, Ti-based MXenes with both homogeneous and mixed terminations are modeled using density functional theory (DFT). An ad hoc modified dispersion correction scheme is used, capable of reproducing the results obtained from a higher level of theory. The nature of the interlayer interactions, comprising van der Waals, dipole-dipole, and hydrogen bonding, is discussed along with the effects of MXene sheet's thickness and C/N ratio. Our results demonstrate that terminations play a major role in regulating MXenes' interlayer and substrate adhesion to iron and iron oxide and, therefore, lubrication, which is also affected by an external load. Using graphene and MoS2 as established references, we verify that MXenes' tribological performance as solid lubricants can be significantly improved by avoiding -OH and -F terminations, which can be done by controlling terminations via post-synthesis processing.

2D MBenes: A Novel Member in the Flatland.

2D MBenes, early transition metal borides, are a very recent derivative of ternary or quaternary transition metal boride (MAB) phases and represent a new member in the flatland. Although holding great potential toward various applications, mainly theoretical knowledge about their potential properties is available. Theoretical calculations and preliminary experimental attempts demonstrate their rich chemistry, excellent reactivity, mechanical strength/stability, electrical conductivity, transition properties, and energy harvesting possibility. Compared to MXenes, MBenes' structure appears to be more complex due to multiple crystallographic arrangements, polymorphism, and structural transformations. This makes their synthesis and subsequent delamination into single flakes challenging. Overcoming this bottleneck will enable a rational control over MBenes' material-structure-property relationship. Innovations in MBenes' postprocessing approaches will allow for the design of new functional systems and devices with multipurpose functionalities thus opening a promising paradigm for the conscious design of high-performance 2D materials.

Roadmap for 2D materials in biotribological/biomedical applications - A review.

The human body involves a large number of systems subjected to contact stresses and thus experiencing wear and degradation. The limited efficacy of existing solutions constantly puts a significant financial burden on the healthcare system, more importantly, patients are suffering due to the complications following a partial or total system failure. More effective strategies are highly dependent on the availability of advanced functional materials demonstrating excellent tribological response and good biocompatibility. In this article, we review the recent progress in implementing two-dimensional (2D) materials into bio-applications involving tribological contacts. We further summarize the current challenges for future progress in the field.

Advanced usage of Ti3C2Tx MXenes for photothermal therapy on different 3D breast cancer models.

Globally, breast cancer is the most diagnosed invasive cancer among women. Current therapies (e.g., chemotherapy) show numerous limitations due to the lack of selectivity and involved side effects, which urgently asks for novel approaches with enhanced tumor-killing efficacy. We previously demonstrated that MXenes, new bioactive nanomaterials with promising photophysical properties, are capable to increase the efficiency of the targeted breast cancer photothermal therapy (PTT). In this work, we investigated the effect of few- and multi-layer Ti3C2Tx MXenes mediated-PTT on two different 3D reliable breast cancer models such as conventional and bio-printed spheroids. We performed PTT on both cancer models using a non-toxic MXene concentration of 50 µg/mL. After PTT, a significant reduction in the cell viability along with a notable increase in reactive oxygen species (ROS) was observed. Moreover, we studied the effect of PTT on the migration of macrophages and endothelial cells toward cancer regions in both 3D models. Our results indicate that PTT mediated by both few- and multi-layer MXenes significantly modulates the tumor progression through cells' death by increasing the temperature, which holds particularly true for the bio-printed model.