A self-organized sandwich structure of chromium nitride for ultra-long lifetime in liquid sodium.

The development of fast neutron reactors with improved efficiency and sustainability, being a tangible solution to the large-scale utilization of nuclear energy, serves as a critical step prior to the commercialization of fusion energy. These reactors use liquid metal coolants, which can weaken the durability of metallic components. Conventional design of protective coatings counts upon thermodynamics, which often overlooks the kinetic factors such as structural evolutions, resulting in deteriorated coating properties. Herein, we present a novel interface-engineering strategy involving the control of the phase transformation direction and interface diffusion reaction. Through iterations of self-organization, desired surfaces and interfaces can be achieved for materials used in harsh environments. Specifically, a CrN-coated steel sample with an interfacial Cr layer was designed and fabricated. After ultra-long (up to 6000 h) immersion in liquid sodium, the CrN/Cr coating structure was converted into a sandwich Cr2N/CrN/Cr2N structure dynamically. As a consequence, the coating system exhibited enhanced properties, namely increased surface hardness (by ∼36%), reduced coefficient of friction (by ∼13%), and enhanced interfacial adhesion (by ∼37%). Thus, the proposed strategy can guide the future design of robust coatings with ultra-long service life in harsh environments.

Charge Density Evolution Governing Interfacial Friction.

It is well-known that the electron nature of a solid in contact plays a predominant role in determining the many properties of the contact systems, but the general rules of electron coupling that govern interfacial friction remain an open issue for the surface/interface community. Here, density functional theory calculations were used to investigate the physical origins of friction of solid interfaces. It was found that interfacial friction can be inherently traced back to the electronic barrier to the change in the contact configuration of the joints in slip due to the resistance of energy level rearrangement leading to electron transfer, which applies for various interface types ranging from van der Waals, metallic, and ionic to covalent joints. The variation of the electron density accompanying contact conformation changes along the sliding pathways is defined to track the frictional energy dissipation process occurring in slip. The results demonstrate that the frictional energy landscapes evolve synchronously with responding charge density evolution along sliding pathways, yielding an explicitly linear dependence of frictional dissipation on electronic evolution. The correlation coefficient enables us to interpret the fundamental concept of shear strength. The present charge evolution model thereby provides insights into the classic hypothesis that the friction force scales with the real contact area. This may shed light on the intrinsic origin of friction at the electronic level, opening the way to the rational design of nanomechanical devices as well as the understanding of the natural faults.

Synthesis and Structure of Water-Soluble Sb Quantum Dots and Enhanced Corrosion Inhibition Performance and Mechanisms.

Generally, single organic or inorganic inhibitors could effectively inhibit corrosion for metallic materials; however, there are rarely reports about the hybrid corrosion inhibitors consisting of organic and inorganic inhibitors. Thus, in this work, we synthesize a hybrid environment-friendly water-soluble corrosion inhibitor (Sb quantum dots) containing Sb, Sb2O3, Sb2O4, and carbon using the electrochemical exfoliation method. The inhibition effectiveness in short- and long-term immersion tests is measured using electrochemical methods, weight loss, and surface analysis. The results exhibit that the corrosion inhibition efficiency sensitively relates to the concentration of Sb quantum dots (SQDs), which achieves the largest value as the concentration of SQDs increases to 200 mg/L. Atomic force microscopy, scanning electron microscopy, and contact angle analysis reveal that the SQDs well-disperse on and cover the Q235 steel surface at 200 mg/L. According to the Langmuir adsorption data, the physicochemical adsorption and effective antioxidation of SQDs on the passivated Q235 steel surface are in charge of the effective corrosion inhibition efficiency in 0.5 M H2SO4 solution.

Superhydrophobic and Self-Healing Mg-Al Layered Double Hydroxide/Silane Composite Coatings on the Mg Alloy Surface with a Long-Term Anti-corrosion Lifetime.

Both a superhydrophobic structure and layered double hydroxide (LDH) coating were effective to improve the corrosion resistance of alloys. In this study, a superhydrophobic composite coating based on LDHs was constructed on Mg alloy by laser treatment, in situ growth of Mg-Al LDHs, and modification with octadecyl-trimethoxy-silane (OTS). The so-obtained composite coating was coded as L-LDHs-OTS, where L stands for laser treatment. Results showed that the L-LDHs-OTS composite coating presented the best anti-corrosion performance and the corrosion current density was reduced by about 5 orders of magnitude compared with that of the Mg alloy substrate. The excellent corrosion resistance was related to the superhydrophobicity of the composite coating, the compactness and ion-exchange capacity of the LDH layer, and the dense Si-O-Si network within the OTS layer. Moreover, the L-LDHs-OTS composite coating was still effective after 20 days of immersion tests, showing good long-term corrosion resistance due to the existence of hydrophobicity of the composite coating and the self-healing ability of LDHs.

Correction: The corrosion behaviors of multilayer diamond-like carbon coatings: influence of deposition periods and corrosive medium.

[This corrects the article DOI: 10.1039/C6RA05527C.].

Correction: Corrosion and tribocorrosion performance of multilayer diamond-like carbon film in NaCl solution.

[This corrects the article DOI: 10.1039/C5RA21207C.].

Contrasting Oxygen Reduction Reactions on Zero- and One-Dimensional Defects of MoS2 for Versatile Applications.

Oxygen reduction reaction (ORR) is a key microscopic process in many electrochemical applications of materials, where the requirements of their ORR performances may vary strikingly, for example, during the uses of MoS2 as an electrocatalyst and anticorrosion/lubricating coating in aqueous/humid environments, ORR should be activated and inhibited, respectively. To reveal a complete ORR profile of MoS2, using first-principles calculations, we examine the stabilities of various possible zero-dimensional point defects on the surface and one-dimensional edge defects and comprehensively explore the ORR activities on pristine MoS2 surface and those defects in acid/alkaline solutions. It is found that the ORRs on the pristine surface and surfaces with point defects always require large overpotentials (>1.0 V), indicating a defect-immune resistance of the planar MoS2 surface against the ORR. However, the ORR overpotentials on edge defects can reach as low as 0.66 V, corresponding to a relatively high activity close to that of the prototypical catalyst Pt (overpotential ∼0.45 V). Such contrasting ORR behaviors of point and edge defects are also understood in depth by analyzing the underlying thermodynamic and electronic-structure mechanisms. This work not only quantitatively explains the performances of MoS2 in both galvanic corrosion and electrochemical catalysis but also provides a useful structure-ORR map that can facilitate adapting the realistic MoS2 to versatile electrochemical applications.

Thermodynamics and kinetics of an oxygen adatom on pristine and functionalized graphene: insight gained into their anticorrosion properties.

The thermodynamic and kinetic stabilities of an O adatom on graphene are critical factors for the formation of oxide defects in graphene, which leads to the breakdown of a graphene protective coating. To systematically understand various behaviors of an O adatom on graphene under the space conditions, the adsorption energies, diffusion paths and barriers, and penetration paths and barriers of the O adatom on pristine and functionalized graphene (e.g., -O, -OH, -H, and -F) are calculated using density functional theory, and the electronic structures are also analyzed in depth to reveal the microscopic mechanisms. We find that chemical functionalization increases both the adsorption stability and diffusion mobility of the O adatom on graphene, implying the possibly exacerbated destructive oxidation and even breakdown of the graphene-based coating. Furthermore, the penetration of the O adatom through pristine and functionalized graphene is also calculated, the occurrence of which is proved to be impossible in reality due to the associated extremely high energetic barriers. The calculated results, revealed mechanisms, and the gained insight into the corrosion resistance of graphene will be helpful for the design, synthesis, and application of related graphene-based protective coatings.

Mutual Identification between the Pressure-Induced Superlubricity and the Image Contrast Inversion of Carbon Nanostructures from AFM Technology.

Previous studies predict pressure-induced superlubricity, but that is still undetermined due to the absence of a probing technique. Here, we present unprecedented mutual identification between the superlubricity and atomic-scale image from atomic force microscopy (AFM) measurement by the first-principles simulation of metallic Cu tip scanning on carbon nanostructures. With decreasing tip height, the sliding potential evolves from anticorrugated, to substantially flattened, and eventually to corrugated patterns, inducing superlubricity of the flattened potential at the critical height. Correspondingly, both the normal forces and the contrast of atomic image patterns also undergo similar inversions at the respective critical tip heights, in accordance with recent experimental observation. On the basis of the underlying mechanism elucidated, the mutual identification between the image contrast inversion and the superlubricity is confirmed. This may advance AFM technology to stimulate the experimental observation of superlubricity from its theoretical studies and may thus promote the development of theory systems of superlubticity.

Novel nitrogen doped carbon dots enhancing the anticorrosive performance of waterborne epoxy coatings.

There are lots of research studies reporting the excellent performances of waterborne epoxy resin coatings to reduce environmental VOC levels. However, it has also been manifested that waterborne epoxy resin coatings do not have high corrosion resistance because of being hydrophilic. Herein, we utilized a kind of N doped carbon dot (N-CD) which has high ethanol solubility and low cytotoxicity to enhance the corrosion resistance of waterborne epoxy resin coatings as a nanofiller. The N-CDs were obtained through a solvothermal method by using 4-aminosalicylic acid (ASA) as a precursor. The diameter and height of N-CDs confirmed by scanning probe microscopy and transmission electron microscopy are 3-5 nm. Corrosion resistance performance of the coatings without and with N-CDs is investigated by electrochemical impedance spectroscopy by immersing them in 3.5 wt% NaCl (aq) for 70 days. The results indicate that the composite coatings with 0.5 wt% N-CDs show superior anticorrosive performance due to bond interactions between N-CDs and polymer chains, the defect repairing effect of N-CDs and the formation of compact Fe2O3 and Fe3O4 passivation layers.

Improvement of anticorrosion ability of epoxy matrix in simulate marine environment by filled with superhydrophobic POSS-GO nanosheets.

Super-hydrophobicity polyhedral oligomeric silsesquioxane-modified graphene oxide (POSS-GO) was synthesized by one-step reaction between graphene oxide (GO) and aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH2). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra indicated that the POSS were successfully connected to the edge and surface of GO nanosheets. Scanning probe microscope (SPM) and transmission electron microscope (TEM) images demonstrated that the POSS-GO with a thickness of 1.58 nm presented a stably dispersion in anhydrous ethanol. Results from electrochemical behaviors showed that the proper incorporation of POSS-GO could availably improve the anticorrosion ability of epoxy based coatings in simulate marine environment (3.5 wt% NaCl solution). The good dispersion of POSS-GO helped to fill the original defect and enhanced the complication of penetration path. The super-hydrophobicity of POSS-GO was beneficial to the reduction of actual contact zone. The synergistic effect of good dispersion and super-hydrophobicity promoted the enhancement of anticorrosion ability for composite coatings.

Superlubricity Enabled by Pressure-Induced Friction Collapse.

From daily intuitions to sophisticated atomic-scale experiments, friction is usually found to increase with normal load. Using first-principle calculations, here we show that the sliding friction of a graphene/graphene system can decrease with increasing normal load and collapse to nearly zero at a critical point. The unusual collapse of friction is attributed to an abnormal transition of the sliding potential energy surface from corrugated, to substantially flattened, and eventually to counter-corrugated states. The energy dissipation during the mutual sliding is thus suppressed sufficiently under the critical pressure. The friction collapse behavior is reproducible for other sliding systems, such as Xe/Cu, Pd/graphite, and MoS2/MoS2, suggesting its universality. The proposed mechanism for diminishing energy corrugation under critical normal load, added to the traditional structural lubricity, enriches our fundamental understanding about superlubricity and isostructural phase transitions and offers a novel means of achieving nearly frictionless sliding interfaces.

Performance evaluation of mercapto functional hybrid silica sol-gel coating and its synergistic effect with f-GNs for corrosion protection of copper surface.

A nanocomposite coating comprising mercapto functional hybrid silica sol-gel coating and functionalized graphene nanoplates nanocomposite coatings with advanced anticorrosive properties was prepared by a sol-gel method. In this study, graphene oxide (GO) nanoplates were silanized using 3-aminopropyltriethoxysilane (APTES) to obtain functional graphene nanoplates (f-GNs). The f-GNs were characterized by FTIR, XRD, XPS, TEM, AFM and TGA techniques. The functionalized graphene nanoplates were chemically bonded to a sol-gel matrix and showed good dispersion in the sol. Then, silica hybrid sol-gel nanocomposites with raw GO and different amounts of f-GNs were applied on the copper surface. Uniform, defect-free and adherent sol-gel films were obtained. Various corresponding methods were used to investigate the nanocomposite coating's properties. The corrosion resistance of copper significantly improved after being coated with mercapto functional hybrid silica sol-gel. The addition of f-GNs to the mercapto functional silica sol-gel coatings further improved the corrosion resistance due to a synergistic effect. Moreover, with an increase in the amount of f-GNs in the nanocomposite coating, the nanocomposite showed improved corrosion resistance. The nanocomposite containing 0.1 wt% f-GNs can efficiently protect the copper substrate from corrosion. This improvement was primarily attributed to the homogeneous dispersion of the f-GNs in the silica gel matrix and their effective barrier against corrosive molecules and ions. However, adding raw GO or excess f-GNs to the silica hybrid sol-gel coating had a negative effect on the corrosion resistance.

Tribological properties of synthetic base oil containing polyhedral oligomeric silsesquioxane grafted graphene oxide.

The dispersion of graphene-based materials in lubricating oil is a prerequisite for improving its friction and wear performance. In this study, polyhedral oligomeric silsesquioxane (POSS) grafted graphene oxide (GO) was synthesized with an aim to improve the dispersibility of graphene in synthetic base oil. The composition and morphology of POSS-GO conjugates were characterized by FTIR, XPS, Raman spectroscopy, TEM and SPM. The tribological behavior of base oil with various concentrations of POSS-GO were examined using a UMT-3 friction and wear tester, and the worn surfaces were analyzed using Raman spectroscopy. It was found that concentrations of POSS-GO additives in the base oil is an important aspect for decreasing the friction and wear of the lubricated solid contacts. At lower and higher concentrations of POSS-GO, the lubricating effect is not effective or even worse. In contrast, at optimized concentration of POSS-GO, graphene sheets could form a boundary tribofilm between the contact, resulting in reduction of the friction coefficient and wear.

Tribological properties of attapulgite/La2O3 nanocomposite as lubricant additive for a steel/steel contact.

Attapulgite is a layered silicate with good friction-reduction and self-repairing properties. In order to further improve its tribological properties, the present work mainly focuses on the preparation of attapulgite/La2O3 nanocomposite and study on its tribological behaviors. The tribological properties of mineral lubricating oil (150SN) containing attapulgite/La2O3 nanocomposite were investigated through an Optimal SRV-IV oscillating friction and wear tester. The rubbing surfaces and generated tribofilms were characterized by SEM, EDS, XPS and nanoindentation. Results indicated that the friction-reducing ability and antiwear property of the oil were both remarkably improved by attapulgite/La2O3 nanocomposite. A tribofilm mainly composed of Fe, Fe3C, FeO, Fe2O3, FeOOH, SiO, SiO2 and organic compound was formed on the rubbing surface under the lubrication of oil with attapulgite/La2O3 nanocomposite. The tribofilm possess excellent self-lubricating ability and mechanical properties, which is responsible for the reduction of friction and wear.

Space irradiation-induced damage to graphene films.

Graphene with impressive electrical, optical, chemical and mechanical properties has promising potential applications for photoelectric devices and mechanical components installed on the space facilities, which will probably face hostile environments including high-energy particulate irradiation. Here we explored the effect of simulated space irradiation on the structure and properties of large-area single-layer and multi-layer graphene films (about four layers) including atomic oxygen (AO), electron (EL) and proton (PR). AO with strong oxidizing capacity reacts with carbon atoms of graphene films and generates carbon dioxide, high-energy PR leads to polymorphic atomic defects in graphene through collision and excitation effects. Miraculously, EL irradiation causes little damage to the graphene films because of the excellent conductivity. Graphene ripples are broken by irradiation and adapt their shape or structure with respect to the substrate via thermodynamic stability, which causes the change of the physical and mechanical properties of graphene.

Multilayer Regulation of Atomic Boron Nitride Films to Improve Oxidation and Corrosion Resistance of Cu.

The boron nitride (BN) monolayer (1L) with high impermeability and resistivity seems to hold promise as a long-term corrosion barrier for Cu under ambient condition, which is supported by recent researches. Here, we perform a complete study of the alternating temperature tests (the sample is exposed in air for 30 days and subsequently heated at 200 °C for 2 h) and electrochemical measurements on 1L and multilayer BN-coated Cu foils. Results imply that the BN-coated Cu foils are less oxidized than uncoated Cu foils after alternating temperature tests, regardless of the layers of BN. Particularly, the oxidation process proceeds slowly in multilayers because most of the underlying defects are covered with BN layers to suppress the oxygen diffusion in the vertical direction and the oxidation mainly occurs on the wrinkled region of BN films. Electrochemical analyses reveal that the BN layers provide an effective physical barrier against the corrosive medium and inhibit the electron diffusion because of their high electrical insulating behavior and the corrosion resistance of the samples increases with increasing BN layers. These findings indicate that BN films with adequate layers are good candidates for oxidation and corrosion protection at the atomic level, which is vital to many industrial and academic applications.

Synergistic effect of hybrid carbon nanotube-graphene oxide as nanoadditive enhancing the frictional properties of ionic liquids in high vacuum.

A remarkable synergetic effect between the graphene oxide (GO) layers and multiwalled carbon nanotubes (MWCNTs) in improving friction and wear on sliding diamond-like carbon (DLC) surfaces under high vacuum condition (10(-5) Pa) and low or high applied load is demonstrated. In tests with sliding DLC surfaces, ionic liquid solution that contains small amounts of GO and MWCNTs exhibited the lowest specific friction coefficient and wear rate under all of the sliding conditions. Optical microscope images of the wear scar of a steel ball showed that GO/MWCNT composites exhibited higher antiwear capability than individual MWCNTs and GO did. Transmission electron microscopy images of nanoadditives after friction testing showed that MWCNTs support the GO layers like pillars and prevent assembly between the GO layers. Their synergistic effect considerably enhances IL-GO/MWCNT composites.

Fabrication of novel graphene-fullerene hybrid lubricating films based on self-assembly for MEMS applications.

The novel graphene-C60 hybrid films have been fabricated successfully on silicon surfaces by a multistep self-assembly process, and showed synergistic effects beyond individual performance in micro/nano-tribological behaviors. It is expected that the graphene-C60 hybrid films may find wide applications as high performance lubricating films in MEMS.

Interface architecture for superthick carbon-based films toward low internal stress and ultrahigh load-bearing capacity.

Superthick diamond-like carbon (DLC) films [(Six-DLC/Siy-DLC)n/DLC] were deposited on 304 stainless steel substrates by using a plane hollow cathode plasma-enhanced chemical vapor deposition method. The structure was investigated by scanning electron microscopy and transmission electron microscopy. Chemical bonding was examined by Raman, Auger electron, and X-ray photoelectron spectroscopy techniques. Mechanical and tribological properties were evaluated using nanoindentation, scratch, interferometry, and reciprocating-sliding friction testing. The results showed that implantation of a silicon ion into the substrate and the architecture of the tensile stress/compressive stress structure decreased the residual stress to almost 0, resulting in deposition of (Six-DLC/Siy-DLC)n/DLC films with a thickness of more than 50 µm. The hardness of the film ranged from 9 to 23 GPa, and the adhesion strength ranged from 4.6 to 57 N depending on the thickness of the film. Friction coefficients were determined in three tested environments, namely, air, water, and oil. Friction coefficients were typically below 0.24 and as low as 0.02 in a water environment. The as-prepared superthick films also showed an ultrahigh load-bearing capacity, and no failure was detected in the reciprocating wear test with contact pressure higher than 3.2 GPa. Reasons for the ultrahigh load-bearing capacity are proposed in combination with the finite-element method.