Multifunctional Aluminum Pre-treatments from End-Functionalized Phosphonic Acid Self-Assembled Monolayers.

Aluminum alloys are used in advanced engineering applications as they possess a combination of favorable properties, including high strength, lightweightness, good corrosion resistance, machineability, and recyclability. Such applications often require forming the sheets into the final components, which is typically aided by an oil-based lubricant, followed by joining them using adhesives, which is hampered by residual lubricant. In this work, aluminum surfaces were modified with different self-assembled monolayers (SAMs), with the goal of significantly reducing the amount of lubricant while simultaneously improving friction properties, forming, and bonding performance. Our results show that SAMs terminated with hydrophilic and nucleophilic end groups give rise to high-energy surfaces with wetting properties that are stable over time. These surfaces showed significantly improved surface wetting by the lubricant, which in turn resulted in an improved forming performance at reduced lubricant coat weights. Moreover, the nucleophilic SAM termination provided outstanding performance in adhesive bonding tests under corrosive conditions.

Angstrom-Scale Transparent Overcoats: Interfacial Nitrogen-Driven Atomic Intermingling Promotes Lubricity and Surface Protection of Ultrathin Carbon.

Lubricity, a phenomenon which enables the ease of motion of objects, and wear resistance, which minimizes material damage or degradation, are important fundamental characteristics for sustainable technology developments. Ultrathin coatings that promote lubricity and wear resistance are of huge importance for a number of applications, including magnetic storage and micro-/nanoelectromechanical systems. Conventional ultrathin coatings have, however, reached their limit. Graphene-based materials that have shown promise to reduce friction and wear have many intrinsic limitations such as high temperature and substrate-specific growth. To address these concerns, a great deal of research is currently ongoing to optimize graphene-based materials. Here we discover that angstrom-thick carbon (8 Å) significantly reduces interfacial friction and wear. This lubricant shows ultrahigh optical transparency and can be directly deposited on a wide range of surfaces at room temperature. Experiments combined with molecular dynamics simulations reveal that the lubricating efficacy of 8 Å carbon is further improved via interfacial nitrogen.

Slippery and Wear-Resistant Surfaces Enabled by Interface Engineered Graphene.

Friction and wear remain the primary cause of mechanical energy dissipation and system failure. Recent studies reveal graphene as a powerful solid lubricant to combat friction and wear. Most of these studies have focused on nanoscale tribology and have been limited to a few specific surfaces. Here, we uncover many unknown aspects of graphene's contact-sliding at micro- and macroscopic tribo-scales over a broader range of surfaces. We discover that graphene's performance reduces for surfaces with increasing roughness. To overcome this, we introduce a new type of graphene/silicon nitride (SiNx, 3 nm) bilayer overcoats that exhibit superior performance compared to native graphene sheets (mono and bilayer), that is, display the lowest microscale friction and wear on a range of tribologically poor flat surfaces. More importantly, two-layer graphene/SiNx bilayer lubricant (<4 nm in total thickness) shows the highest macroscale wear durability on tape-head (topologically variant surface) that exceeds most previous thicker (∼7-100 nm) overcoats. Detailed nanoscale characterization and atomistic simulations explain the origin of the reduced friction and wear arising from these nanoscale coatings. Overall, this study demonstrates that engineered graphene-based coatings can outperform conventional coatings in a number of technologies.

Spontaneous formation of a self-healing carbon nanoskin at the liquid-liquid interface.

Biological membranes exhibit the ability to self-repair and dynamically change their shape while remaining impermeable. Yet, these defining features are difficult to reconcile with mechanical robustness. Here, we report on the spontaneous formation of a carbon nanoskin at the oil-water interface that uniquely combines self-healing attributes with high stiffness. Upon the diffusion-controlled self-assembly of a reactive molecular surfactant at the interface, a solid elastic membrane forms within seconds and evolves into a continuous carbon monolayer with a thickness of a few nanometers. This nanoskin has a stiffness typical for a 2D carbon material with an elastic modulus in bending of more than 40-100 GPa; while brittle, it shows the ability to self-heal upon rupture, can be reversibly reshaped, and sustains complex shapes. We anticipate such an unusual 2D carbon nanomaterial to inspire novel approaches towards the formation of synthetic cells with rigid shells, additive manufacturing of composites, and compartmentalization in industrial catalysis.

Boosting contact sliding and wear protection via atomic intermixing and tailoring of nanoscale interfaces.

Friction and wear cause energy wastage and system failure. Usually, thicker overcoats serve to combat such tribological concerns, but in many contact sliding systems, their large thickness hinders active components of the systems, degrades functionality, and constitutes a major barrier for technological developments. While sub-10-nm overcoats are of key interest, traditional overcoats suffer from rapid wear and degradation at this thickness regime. Using an enhanced atomic intermixing approach, we develop a ~7- to 8-nm-thick carbon/silicon nitride (C/SiN x ) multilayer overcoat demonstrating extremely high wear resistance and low friction at all tribological length scales, yielding ~2 to 10 times better macroscale wear durability than previously reported thicker (~20 to 100 nm) overcoats on tape drive heads. We report the discovery of many fundamental parameters that govern contact sliding and reveal how tuning atomic intermixing at interfaces and varying carbon and SiN x thicknesses strongly affect friction and wear, which are crucial for advancing numerous technologies.

Superior wear resistance and low friction in hybrid ultrathin silicon nitride/carbon films: synergy of the interfacial chemistry and carbon microstructure.

Amorphous carbon-based films are commonly investigated as protective nanocoatings in macro- to nano-scale devices due to their exceptional tribological and mechanical properties. However, with further device miniaturization where even thinner coatings are required, the wear durability of the nanocoating rapidly degrades at the expense of lower thickness. Here we discover that for sub-10 nm coating thicknesses, a hybrid bi-layer film structure, comprising a high sp3-bonded amorphous carbon top layer and a silicon nitride (SiNx) bottom layer, consistently outperforms its single-layer amorphous carbon counterpart in terms of wear durability on a commercial tape drive head, while exhibiting low, stable friction and excellent wear resistance on a flat ceramic substrate. The superior performance of the hybrid film is attributed to the constructive synergy of the sp3-rich carbon microstructure and an enhanced interfacial chemistry arising from additional interfacial bonding. Moreover, a high energy C+ ion treatment step, introduced either directly to the substrate or to the SiNx layer before carbon deposition, also aids in increasing atomic mixing that contributes to further improvement in the wear resistance. This study highlights the importance of both the carbon microstructure and interfacial chemistry in the design of wear-durable nanocoatings at few-nanometer thicknesses, particularly for aggressive wear conditions.

Atomic Scale Interface Manipulation, Structural Engineering, and Their Impact on Ultrathin Carbon Films in Controlling Wear, Friction, and Corrosion.

Reducing friction, wear, and corrosion of diverse materials/devices using <2 nm thick protective carbon films remains challenging, which limits the developments of many technologies, such as magnetic data storage systems. Here, we present a novel approach based on atomic scale interface manipulation to engineer and control the friction, wear, corrosion, and structural characteristics of 0.7-1.7 nm carbon-based films on CoCrPt:oxide-based magnetic media. We demonstrate that when an atomically thin (∼0.5 nm) chromium nitride (CrNx) layer is sandwiched between the magnetic media and an ultrathin carbon overlayer (1.2 nm), it modifies the film-substrate interface, creates various types of interfacial bonding, increases the interfacial adhesion, and tunes the structure of carbon in terms of its sp(3) bonding. These contribute to its remarkable functional properties, such as stable and lowest coefficient of friction (∼0.15-0.2), highest wear resistance and better corrosion resistance despite being only ∼1.7 nm thick, surpassing those of ∼2.7 nm thick current commercial carbon overcoat (COC) and other overcoats in this work. While this approach has direct implications for advancing current magnetic storage technology with its ultralow thickness, it can also be applied to advance the protective and barrier capabilities of other ultrathin materials for associated technologies.

Understanding the role of nitrogen in plasma-assisted surface modification of magnetic recording media with and without ultrathin carbon overcoats.

A novel scheme of pre-surface modification of media using mixed argon-nitrogen plasma is proposed to improve the protection performance of 1.5 nm carbon overcoats (COC) on media produced by a facile pulsed DC sputtering technique. We observe stable and lower friction, higher wear resistance, higher oxidation resistance, and lower surface polarity for the media sample modified in 70%Ar + 30%N2 plasma and possessing 1.5 nm COC as compared to samples prepared using gaseous compositions of 100%Ar and 50%Ar + 50%N2 with 1.5 nm COC. Raman and X-ray photoelectron spectroscopy results suggest that the surface modification process does not affect the microstructure of the grown COC. Instead, the improved tribological, corrosion-resistant and oxidation-resistant characteristics after 70%Ar + 30%N2 plasma-assisted modification can be attributed to, firstly, the enrichment in surface and interfacial bonding, leading to interfacial strength, and secondly, more effective removal of ambient oxygen from the media surface, leading to stronger adhesion of the COC with media, reduction of media corrosion and oxidation, and surface polarity. Moreover, the tribological, corrosion and surface properties of mixed Ar + N2 plasma treated media with 1.5 nm COCs are found to be comparable or better than ~2.7 nm thick conventional COC in commercial media.

Ultrathin Carbon with Interspersed Graphene/Fullerene-like Nanostructures: A Durable Protective Overcoat for High Density Magnetic Storage.

One of the key issues for future hard disk drive technology is to design and develop ultrathin (<2 nm) overcoats with excellent wear- and corrosion protection and high thermal stability. Forming carbon overcoats (COCs) having interspersed nanostructures by the filtered cathodic vacuum arc (FCVA) process can be an effective approach to achieve the desired target. In this work, by employing a novel bi-level surface modification approach using FCVA, the formation of a high sp(3) bonded ultrathin (~1.7 nm) amorphous carbon overcoat with interspersed graphene/fullerene-like nanostructures, grown on magnetic hard disk media, is reported. The in-depth spectroscopic and microscopic analyses by high resolution transmission electron microscopy, scanning tunneling microscopy, time-of-flight secondary ion mass spectrometry, and Raman spectroscopy support the observed findings. Despite a reduction of ~37% in COC thickness, the FCVA-processed thinner COC (~1.7 nm) shows promising functional performance in terms of lower coefficient of friction (~0.25), higher wear resistance, lower surface energy, excellent hydrophobicity and similar/better oxidation corrosion resistance than current commercial COCs of thickness ~2.7 nm. The surface and tribological properties of FCVA-deposited COC was further improved after deposition of lubricant layer.

Probing the role of carbon microstructure on the thermal stability and performance of ultrathin (<2 nm) overcoats on L10 FePt media for heat-assisted magnetic recording.

An understanding of the factors influencing the thermal stability of ultrathin carbon overcoats (COCs) is crucial for their application in heat-assisted magnetic recording (HAMR) at densities ≥ 1 Tb/in(2). Two types of non-hydrogenated ultrathin (∼1.5 nm) COCs were investigated after being subjected to laser-induced localized heating (at temperatures > 700 K) as envisaged in HAMR. Filtered cathodic vacuum arc (FCVA)-processed carbon with tuned C(+) ion energies of 350 eV followed by 90 eV provides significantly higher sp(3) C-C hybridization than magnetron sputter deposition even at very low thicknesses of ∼1.5 nm. As a result, the FCVA-deposited ultrathin carbon overcoats displayed excellent thermal stability along with improved wear and corrosion resistance. On the other hand, the sputtered carbon exhibited carbon loss and topographical and structural changes after laser irradiation owing to lower sp(3) hybridization. Therefore, this study highlights the pivotal role of carbon microstructure, primarily sp(3) hybridization, in non-hydrogenated carbon overcoats to maintain excellent thermal stability during the recurring high-temperature cycles in a HAMR process.

Probing the role of an atomically thin SiNx interlayer on the structure of ultrathin carbon films.

Filtered cathodic vacuum arc (FCVA) processed carbon films are being considered as a promising protective media overcoat material for future hard disk drives (HDDs). However, at ultrathin film levels, FCVA-deposited carbon films show a dramatic change in their structure in terms of loss of sp3 bonding, density, wear resistance etc., compared to their bulk counterpart. We report for the first time how an atomically thin (0.4 nm) silicon nitride (SiNx) interlayer helps in maintaining/improving the sp3 carbon bonding, enhancing interfacial strength/bonding, improving oxidation/corrosion resistance, and strengthening the tribological properties of FCVA-deposited carbon films, even at ultrathin levels (1.2 nm). We propose the role of the SiNx interlayer in preventing the catalytic activity of Co and Pt in media, leading to enhanced sp3C bonding (relative enhancement~40%). These findings are extremely important in view of the atomic level understanding of structural modification and the development of high density HDDs.

Enhanced tribological, corrosion, and microstructural properties of an ultrathin (<2 nm) silicon nitride/carbon bilayer overcoat for high density magnetic storage.

An ultrathin bilayer overcoat of silicon nitride and carbon (SiNx/C) providing low friction, high wear resistance, and high corrosion resistance is proposed for future generation hard disk media. The 16 Å thick SiNx/C overcoat consists of an atomically thin SiNx underlayer (4 Å) and a carbon layer (12 Å), fabricated by reactive magnetron sputtering and filtered cathodic vacuum arc (FCVA), respectively. When compared with monolithic overcoats of FCVA-deposited carbon (16 Å) and sputtered SiNx (16 Å), the SiNx/C bilayer overcoat demonstrated the best tribological performance with a coefficient of friction < 0.2. Despite showing marginally less electrochemical corrosion protection than monolithic SiNx, its ability to protect the magnetic media from corrosion/oxidation was better than that of an ∼27 Å thick commercial hard disk overcoat and 16 Å thick monolithic FCVA-deposited carbon. From X-ray photoelectron spectroscopy and Raman spectroscopy analyses, it was found that the introduction of the 4 Å SiNx underlayer facilitated higher sp(3) hybridization within the carbon layer by acting as a barrier and promoted the formation of strong bonds at the SiNx/C and the SiNx/media interfaces by acting as an adhesion layer. The higher sp(3) carbon content is expected to improve the thermal stability of the overcoat, which is extremely important for future hard disk drives employing heat assisted magnetic recording (HAMR).