Multifunctional Applications Enabled by Fluorination of Hexagonal Boron Nitride.

2D materials exhibit exceptional properties as compared to their macroscopic counterparts, with promising applications in nearly every area of science and technology. To unlock further functionality, the chemical functionalization of 2D structures is a powerful technique that enables tunability and new properties within these materials. Here, the successful effort to chemically functionalize hexagonal boron nitride (hBN), a chemically inert 2D ceramic with weak interlayer forces, using a gas-phase fluorination process is exploited. The fluorine functionalization guides interlayer expansion and increased polar surface charges on the hBN sheets resulting in a number of vastly improved applications. Specifically, the F-hBN exhibits enhanced dispersibility and thermal conductivity at higher temperatures by more than 75% offering exceptional performance as a thermofluid additive. Dispersion of low volumes of F-hBN in lubricating oils also offers marked improvements in lubrication and wear resistance for steel tribological contacts decreasing friction by 31% and wear by 71%. Additionally, incorporating numerous negatively charged fluorine atoms on hBN induces a permanent dipole moment, demonstrating its applicability in microelectronic device applications. The findings suggest that anchoring chemical functionalities to hBN moieties improves a variety of properties for h-BN, making it suitable for numerous other applications such as fillers or reinforcement agents and developing high-performance composite structures.

Fatigue of graphene.

Materials can suffer mechanical fatigue when subjected to cyclic loading at stress levels much lower than the ultimate tensile strength, and understanding this behaviour is critical to evaluating long-term dynamic reliability. The fatigue life and damage mechanisms of two-dimensional (2D) materials, of interest for mechanical and electronic applications, are currently unknown. Here, we present a fatigue study of freestanding 2D materials, specifically graphene and graphene oxide (GO). Using atomic force microscopy, monolayer and few-layer graphene were found to exhibit a fatigue life of more than 109 cycles at a mean stress of 71 GPa and a stress range of 5.6 GPa, higher than any material reported so far. Fatigue failure in monolayer graphene is global and catastrophic without progressive damage, while molecular dynamics simulations reveal this is preceded by stress-mediated bond reconfigurations near defective sites. Conversely, functional groups in GO impart a local and progressive fatigue damage mechanism. This study not only provides fundamental insights into the fatigue enhancement behaviour of graphene-embedded nanocomposites, but also serves as a starting point for the dynamic reliability evaluation of other 2D materials.

Surface and Mechanical Characterization of Dental Yttria-Stabilized Tetragonal Zirconia Polycrystals (3Y-TZP) After Different Aging Processes.

Yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) is a ceramic material used in indirect dental restorations. However, phase transformation at body temperature may compromise the material's mechanical properties, affecting the clinical performance of the restoration. The effect of mastication on 3Y-TZP aging has not been investigated. 3Y-TZP specimens (IPS E-max ZirCAD and Z5) were aged in three different modes (n=13): no aging (control), hydrothermal aging (HA), or chewing simulation (CS). Mechanical properties and surface topography were analyzed. Analysis of variance showed that neither aging protocol (p=0.692) nor material (p=0.283) or the interaction between them (p=0.216) had a significant effect on flexural strength, values ranged from 928.8 MPa (IPSHA) to 1,080.6 MPa (Z5HA). Nanoindentation analysis showed that material, aging protocol, and the interaction between them had a significant effect (p<0.001) on surface hardness and reduced Young's modulus. The compositional analysis revealed similar yttrium content for all the experimental conditions (aging: p=0.997; material: p=0.248; interaction material×aging: p=0.720). Atomic force microscopy showed an effect of aging protocols on phase transformation, with samples submitted to CS exhibiting features compatible with maximized phase transformation, such as increased volume of the material microstructure at the surface leading to an increase in surface roughness.

Effect of Humidity and Water Intercalation on the Tribological Behavior of Graphene and Graphene Oxide.

In this work, the effect of humidity and water intercalation on the friction and wear behavior of few-layers of graphene and graphene oxide (GO) was studied using friction force microscopy. Thickness measurements demonstrated significant water intercalation within GO affecting its surface topography (roughness and protrusions), whereas negligible water intercalation of graphene was observed. It was found that water intercalation in GO contributed to wearing of layers at a relative humidity as low as ∼30%. The influence of surface wettability and water adsorption was also studied by comparing the sliding behavior of SiO2/GO, SiO2/Graphene, and SiO2/SiO2 interfaces. Friction for the SiO2/GO interface increased with relative humidity due to water intercalation and condensation of water. In contrast, it was observed that adsorption of water molecules lubricated the SiO2/SiO2 interface due to easy shearing of water on the hydrophobic surface, particularly once the adsorbed water layers had transitioned from "ice-like water" to "liquid-like water" structures. Lastly, an opposite friction trend was observed for the graphene/SiO2 interface with water molecules failing to lubricate the interface as compared to the dry graphene/SiO2 contact.

Tribochemical Competition within a MoS2/Ti Dry Lubricated Macroscale Contact in Ultrahigh Vacuum: A Time-of-Flight Secondary Ion Mass Spectrometry Investigation.

Controlling and predicting the tribological behavior of dry lubricants is a necessity to ensure low friction, long life, and low particle generation. Understanding the tribochemistry of the materials as a function of the environment is of primary interest as synergistic effects exist between the mechanics, the physicochemistry, and the thermodynamics within a contact. However, in most studies the role of the coating internal contaminants in the process is often discarded to the benefit of a more common approach in which the performances of the materials are compared as a function of different atmospheric pressure environments. The study focuses on the understanding of the tribochemical processes occurring between the materials and their internal contaminants inside an AISI440C contact lubricated by a MoS2/Ti coating. Time-of-flight secondary ion mass spectrometry is used to study at the molecular level, the material before and after friction. Friction tests with different durations are performed in ultrahigh vacuum at the macroscale to stay relevant to the real application (space). The adsorption/desorption of gaseous species during friction is monitored by mass spectrometry to ensure reliable study of the tribochemical processes inside the contact. The study shows that a competition exists between the Ti- and MoS2-based materials to create the appropriate lubricating materials via (i) recrystallization of MoS2 materials with creation of a MoS xO y material via reactions with internal contaminants (presumably H2O), (ii) reaction of Ti-based materials with internal contaminants (mostly H2O and N2). The biphasic material created is highly similar to the one created in both humid air and dry N2 environments and providing low friction and low particle generation. However, the process is incomplete. The study thus brings insight into the possibility of controlling friction via a rational inclusion of reactants in a form of contaminants to control the tribochemical processes governing the low friction and long life.

An Insight into the Phase Transformation of WS2 upon Fluorination.

The transformation from semiconducting to metallic phase, accompanied by a structural transition in 2D transition metal dichalcogenides has attracted the attention of the researchers worldwide. The unconventional structural transformation of fluorinated WS2 (FWS2 ) into the 1T phase is described. The energy difference between the two phases debugs this transition, as fluorination enhances the stability of 1T FWS2 and makes it energetically favorable at higher F concentration. Investigation of the electronic and optical nature of FWS2 is supplemented by possible band structures and bandgap calculations. Magnetic centers in the 1T phase appear in FWS2 possibly due to the introduction of defect sites. A direct consequence of the phase transition and associated increase in interlayer spacing is a change in friction behavior. Friction force microscopy is used to determine this effect of functionalization accompanied phase transformation.

Ultrafast, sensitive and large-volume on-chip real-time PCR for the molecular diagnosis of bacterial and viral infections.

To control future infectious disease outbreaks, like the 2014 Ebola epidemic, it is necessary to develop ultrafast molecular assays enabling rapid and sensitive diagnoses. To that end, several ultrafast real-time PCR systems have been previously developed, but they present issues that hinder their wide adoption, notably regarding their sensitivity and detection volume. An ultrafast, sensitive and large-volume real-time PCR system based on microfluidic thermalization is presented herein. The method is based on the circulation of pre-heated liquids in a microfluidic chip that thermalize the PCR chamber by diffusion and ultrafast flow switches. The system can achieve up to 30 real-time PCR cycles in around 2 minutes, which makes it the fastest PCR thermalization system for regular sample volume to the best of our knowledge. After biochemical optimization, anthrax and Ebola simulating agents could be respectively detected by a real-time PCR in 7 minutes and a reverse transcription real-time PCR in 7.5 minutes. These detections are respectively 6.4 and 7.2 times faster than with an off-the-shelf apparatus, while conserving real-time PCR sample volume, efficiency, selectivity and sensitivity. The high-speed thermalization also enabled us to perform sharp melting curve analyses in only 20 s and to discriminate amplicons of different lengths by rapid real-time PCR. This real-time PCR microfluidic thermalization system is cost-effective, versatile and can be then further developed for point-of-care, multiplexed, ultrafast and highly sensitive molecular diagnoses of bacterial and viral diseases.

New family of fluorinated polymer chips for droplet and organic solvent microfluidics.

We present a new family of microfluidic chips hot embossed from a commercial fluorinated thermoplastic polymer (Dyneon THV). This material shares most of the properties of fluoro polymers (very low surface energy and resistance to chemicals), but is easier to process due to its relatively low melting point. Finally, as an elastic material it also allows easy world to chip connections. Fluoropolymer films can be imprinted by hot embossing from PDMS molds prepared by soft lithography. Chips are then sealed by an original technique (termed Monolithic-Adhesive-Bonding), using two different grades of fluoropolymer to obtain uniform mechanical, chemical and surface properties. This fabrication process is well adapted to rapid prototyping, but it also has potential for low cost industrial production, since it does not require any curing or etching step. We prepared microfluidic devices with micrometre resolution features, that are optically transparent, and that provide good resistance to pressure (up to 50 kPa). We demonstrated the transport of water droplets in fluorinated oil, and fluorescence detection of DNA within the droplets. No measurable interaction of the droplets with the channels wall was observed, alleviating the need for surface treatment previously necessary for droplet applications in microfluidic chips. These chips can also handle harsh organic solvents. For instance, we demonstrated the formation of chloroform droplets in fluorinated oil, expanding the potential for on chip microchemistry.