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Humidity‐Resistant Ultralow Friction in Diamond‐Like Carbon Coatings Enabled by Graphitic Nanodiamonds

MetadataDetails
Publication Date2025-06-23
JournalSmall Structures
AuthorsAndrea Mescola, Giovanni Bertoni, Gian Carlo Gazzadi, Michał Bartkowski, Adalberto Camisasca
InstitutionsIstituto Nanoscienze, Dublin City University
Citations2
AnalysisFull AI Review Included

Executive Summary: Humidity-Resistant Ultralow Friction in Diamond-Like Carbon Coatings

Section titled “Executive Summary: Humidity-Resistant Ultralow Friction in Diamond-Like Carbon Coatings”

This research demonstrates a robust, scalable method for achieving humidity-resistant ultralow friction (CoF < 0.1) on industrial Diamond-Like Carbon (DLC) coatings using Graphitic Nanodiamonds (Gr-NDs).

  • Ultralow Friction Achieved: Coefficient of Friction (CoF) stabilized at ≈0.09 in humid air (RH 50%-60%) and ≈0.07 in dry N2 (RH 15%) environments, overcoming a critical limitation of traditional DLC tribology.
  • Core-Shell Mechanism: The superior performance is attributed to the pre-synthesized core-shell structure of Gr-NDs (sp3 diamond core wrapped in few-layer sp2 graphene).
  • Robust Transfer Layer (TL): Gr-NDs promote the in operando formation of a highly structured, graphitic transfer layer (TL-I) on the steel counterpart.
  • Tribochemical Stabilization: Detailed EELS analysis confirms that moderate tribochemical oxidation stabilizes the TL-I via the formation of oxygen-containing functional groups (C-O-C, C-OH), which facilitate water-mediated lubrication.
  • Superior Wear Resistance: The use of Gr-NDs drastically reduced wear volume (0.57 x 10-4 mm3) compared to conventional functionalization methods (GFs + NDs).
  • Scalability: The approach utilizes industrial-level DLC coatings and a simple drop-casting functionalization method, making it highly relevant for demanding mechanical applications.

The following hard data points were extracted from the tribological and material characterization results:

ParameterValueUnitContext
Coefficient of Friction (Humid)0.09-Gr-NDs functionalization (RH 50%-60%)
Coefficient of Friction (Dry)0.07-Gr-NDs functionalization (RH 15%)
Relative Humidity (Humid Test)50-60%Standard ambient air conditions
Relative Humidity (Dry Test)15%Dry N2 atmosphere
H-DLC Coating Thickness2.5µmHydrogenated amorphous carbon (a-C:H)
H-DLC Hardness2600HvManufacturer specification
Normal Load1NBall-on-disc tribometer test
Maximum Hertzian Contact Pressure≈0.8GPaCalculated value
Gr-ND Synthesis Temperature1300°CThermal annealing of pristine NDs (He atmosphere)
TL-I sp2 Carbon Fraction49%Measured via EELS C-K edge analysis
Wear Volume (Gr-NDs)0.57 x 10-4mm3Removed volume from 100Cr6 steel counterpart
TL-I Thickness (Average)≈68 ± 13nmMeasured via EELS log-ratio method

The experimental procedure focused on the synthesis of the core-shell nanostructures and their integration onto industrial DLC substrates for tribological testing.

  1. DLC Substrate Deposition: Hydrogenated Diamond-Like Carbon (H-DLC) coatings (a-C:H, 2.5 µm thick) were deposited on metal substrates (AlSi10Mg with buffer layers) using industrial Plasma-Assisted Chemical Vapor Deposition (PA-CVD) at 250 °C.
  2. Graphitic Nanodiamond (Gr-ND) Synthesis: Pristine Nanodiamonds (NDs, 4-6 nm) were thermally annealed at a high temperature (1300 °C) for 60 minutes under a controlled Helium (He) atmosphere.
  3. Carbon Nano-Onion (CNO) Synthesis (Reference): CNOs (fully sp2 graphitized) were synthesized by annealing NDs at 1650 °C under a Helium atmosphere.
  4. Substrate Functionalization: Nanostructures were suspended in isopropanol (1 mg mL-1) and consecutively drop-cast onto the DLC substrates (total loading of 0.420 mg per 15 cm2).
  5. Drying: Samples were dried under nitrogen (N2) flow to ensure complete solvent removal.
  6. Tribological Testing: Tests were performed using a ball-on-disc tribometer against a 4 mm 100Cr6 steel ball counterpart under a 1 N normal load (linear velocity 10 cm s-1).
  7. Environmental Control: Tests were conducted in two controlled environments: Humid Air (RH 50%-60%) and Dry N2 (RH 15%).
  8. Transfer Layer Analysis: Cross-sectional lamellae of the resulting transfer layers (TLs) were prepared using Focused Ion Beam (FIB) lift-out technique and analyzed via HRTEM, Raman spectroscopy, and spatially resolved Electron Energy-Loss Spectroscopy (EELS).

The research highlights the critical role of high-quality diamond nanostructures and robust carbon coatings in achieving advanced tribological performance, particularly under challenging humid conditions. 6CCVD, as an expert supplier of MPCVD diamond materials, is uniquely positioned to support the replication and extension of this groundbreaking research.

Applicable Materials for Advanced Tribology Research

Section titled “Applicable Materials for Advanced Tribology Research”

While the paper utilized industrial H-DLC, the core mechanism relies on the stability and purity of the diamond (sp3) core of the Gr-NDs. For researchers seeking superior control and purity in their base materials or functionalization precursors, 6CCVD recommends:

  • High-Purity Polycrystalline Diamond (PCD):
    • Application: Ideal substrates for large-area functionalization studies, offering superior thermal and mechanical stability compared to industrial DLC.
    • Capability Match: 6CCVD supplies PCD plates/wafers up to 125 mm in diameter, enabling large-scale testing and industrial prototyping.
  • Single Crystal Diamond (SCD) Plates:
    • Application: For fundamental studies requiring ultra-low defect density and highly controlled surface chemistry, especially for investigating the initial formation kinetics of the transfer layer (TL).
    • Capability Match: SCD available in thicknesses from 0.1 µm to 500 µm with ultra-smooth polishing (Ra < 1 nm).
  • Custom Diamond Precursors:
    • Application: While 6CCVD does not supply the Gr-NDs directly, we provide high-purity, high-quality MPCVD diamond material that can serve as a superior precursor for synthesizing custom nanodiamonds or for use as a counter-surface in tribological systems.

The integration of functionalized carbon materials into real-world mechanical and electronic systems often requires precise dimensions and specialized interfaces.

Research Requirement6CCVD Customization CapabilityValue Proposition
Substrate DimensionsCustom plates/wafers up to 125 mm (PCD) and custom laser cutting services.Allows scaling from laboratory discs (45 mm used in paper) to industrial-sized components.
Interface EngineeringInternal metalization capabilities: Au, Pt, Pd, Ti, W, Cu deposition.Essential for integrating functionalized diamond layers into MEMS, sensors, or electrochemical electrodes where the tribological layer must also serve as a conductive interface.
Surface FinishPolishing down to Ra < 1 nm (SCD) and Ra < 5 nm (Inch-size PCD).Provides ultra-flat substrates necessary for advanced fundamental studies of superlubricity and transfer layer formation kinetics.
Thickness ControlSCD/PCD layers available from 0.1 µm to 500 µm, and substrates up to 10 mm.Enables precise control over the mechanical properties and thermal management of the final tribological system.
  • In-House PhD Team: 6CCVD’s engineering team, composed of PhD-level material scientists, offers expert consultation on material selection, surface preparation, and integration strategies for humidity-resistant tribological projects and similar advanced carbon functionalization applications.
  • Global Supply Chain: We ensure reliable, global delivery of custom diamond materials, with DDU (Delivered Duty Unpaid) as the default shipping method and DDP (Delivered Duty Paid) available upon request.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

Hydrogenated diamond‐like carbon (H‐DLC) coatings are extensively employed in high‐performance tribological applications, yet their frictional behavior in humid environments remains a critical limitation. A scalable and industrially viable strategy based on graphitic nanodiamonds (Gr‐NDs) is here proposed, enabling humidity‐resistant ultralow friction (coefficient of friction <0.1) without requiring controlled atmospheres or complex surface treatments. This approach is distinct from many recent methods involving the deposition of nanoparticles and 2D materials, which often fail under humid conditions. Gr‐NDs leverage their intrinsic core-shell nanostructure to promote the in operando formation of a peculiar graphitic transfer layer (TL), directly enhancing interfacial lubrication. High‐resolution transmission electron microscopy and Raman spectroscopy confirm that these nanostructures are effectively retained within the TL, ensuring superior wear resistance and friction reduction. Furthermore, spectroscopic analysis reveals that moderate tribochemical oxidation stabilizes the TL, extending its durability under realistic operating conditions. This work establishes Gr‐NDs as a disruptive functional additive for H‐DLC coatings, offering a robust, scalable, and environmentally friendly solution for next‐generation tribological systems in demanding mechanical applications.