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Influence of parameters in the magnetron sputtering process (HiPIMS) on the mechanical and antibacterial properties of silver-doped DLC coatings

MetadataDetails
Publication Date2025-05-20
JournalArchives of Civil and Mechanical Engineering
AuthorsArtur Albert Kozera, Z. SƂomka, Joanna KacprzyƄska-GoƂacka, RafaƂ ChoduƄ, Daniel Paćko
AnalysisFull AI Review Included

This study investigates the optimization of silver-doped Diamond-Like Carbon (DLC) coatings (Cr-CrN-DLC(Ag)) deposited on 316L steel using High-Power Impulse Magnetron Sputtering (HiPIMS) for enhanced mechanical and antibacterial performance.

  • Core Achievement: Successfully controlled the silver concentration in the DLC matrix (0.3% to 16%) by varying the Ag target magnetron pulse frequency (200 Hz to 800 Hz).
  • Antibacterial Efficacy: All silver-doped coatings demonstrated 100% bactericidal activity against both Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) under static contact conditions.
  • Structural Impact: Increased silver content led to a decrease in the sp3/sp2 hybridization ratio of the carbon matrix, resulting in structural disorder and the formation of soft metallic phases.
  • Mechanical Trade-off: Hardness decreased significantly with increasing silver content (from ~15 GPa for pure DLC to ~4 GPa for 800 Hz Ag-doped).
  • Optimal Formulation: The DLC(Ag)-200 Hz coating (0.3% Ag) provided the best balance, retaining high mechanical properties (Hardness ~12 GPa) while ensuring complete bactericidal activity.
  • Process Stability: HiPIMS provided stable deposition, protecting the targets from poisoning and ensuring a compact microstructure with good adhesion.
ParameterValueUnitContext
Substrate Material316LSteelBase material
Deposition MethodHiPIMSN/AHigh-Power Impulse Magnetron Sputtering
Deposition TemperatureBelow 200°CProcess temperature
Ag Target Pulse Frequency Range200 to 800HzControlled variable for Ag content
Ag Content (200 Hz)0.3%Lowest concentration, optimal coating
Ag Content (800 Hz)16%Highest concentration
Hardness (Pure DLC)~15GPaReference coating
Hardness (DLC(Ag)-200 Hz)~12GPaBest mechanical properties among doped samples
Hardness (DLC(Ag)-800 Hz)~4GPaLowest hardness
Young’s Modulus Range150-220GPaRange for all doped coatings
Adhesion Critical Load Fc2 (DLC(Ag)-200 Hz)15NFirst adhesive defects (latest appearance)
Adhesion Critical Load Fc3 (DLC(Ag)-200 Hz)24NTotal delamination (earliest occurrence)
Graphite Target Power P19.24kWConstant power supply
Silver Target Power P20.36kWConstant power supply
Graphite Target Pulse Duration t160”sConstant parameter
Silver Target Pulse Duration t230”sConstant parameter
Bactericidal Efficacy100%Against E. coli and S. aureus for all Ag-doped samples

The multilayer Cr-CrN-DLC(Ag) coatings were deposited using a custom-built HiPIMS system featuring three circular magnetrons (Chromium, Graphite, Silver).

  1. Substrate Preparation: 316L steel substrates were heated to 200 °C and subjected to ion-etching using Cr+ plasma to ensure surface cleanliness and enhance adhesion.
  2. Interlayer Deposition: Cr and CrN layers were deposited sequentially to serve as adhesion-promoting interlayers between the steel substrate and the DLC top layer.
  3. DLC Matrix Deposition: The graphite target magnetron was operated at constant parameters: 9.24 kW power, 60 ”s pulse duration, and 1000 Hz frequency.
  4. Silver Doping Control: The silver target magnetron was operated at a constant power of 0.36 kW and a pulse duration of 30 ”s. The silver content was precisely modulated by varying the voltage pulse frequency (200, 400, 600, and 800 Hz), which controlled the number of Ag ions reaching the substrate.
  5. Morphological Analysis: Surface morphology was analyzed using Light Microscopy (Keyence VHX1000E) and Scanning Electron Microscopy (HITACHI TM3000).
  6. Compositional Analysis: Elemental analysis (Ag concentration) was performed using Energy Dispersive Spectroscopy (EDS). Phase composition (sp3/sp2 ratio) was determined via Raman spectroscopy (JASCO NRS—5100).
  7. Mechanical Testing: Hardness and Young’s modulus were measured using nanoindentation, ensuring indentation depth did not exceed 10% of the total coating thickness. Adhesion was assessed via the scratch test (REVETEST CSM) to determine critical loads (Fc1, Fc2, Fc3).
  8. Antibacterial Testing: Bactericidal activity was measured using the static contact method against E. coli and S. aureus over 24 hours, simulating conditions conducive to biofilm formation.

The development of mechanically robust, fully bactericidal DLC coatings is highly relevant for industries requiring durable, hygienic surfaces.

  • Medical and Healthcare:
    • Surgical Implants: Coating 316L stainless steel orthopedic implants (e.g., screws, pins, joint replacements) to prevent bacterial colonization and reduce the risk of antimicrobial-resistant infections.
    • Medical Instruments: Application on reusable surgical tools and diagnostic equipment to maintain sterility and high wear resistance during repeated sterilization cycles.
  • Consumer Goods and Public Spaces:
    • High-Touch Surfaces: Coating handles, railings, and public transport components where frequent contact necessitates continuous antimicrobial protection combined with scratch resistance.
  • Industrial and Manufacturing:
    • Food and Beverage Processing: Coating machinery and contact surfaces in food production lines to meet stringent hygiene standards and resist chemical cleaning agents.
    • Fluid Handling: Application on pump components, valves, and seals in water treatment or chemical processing where both antiwear properties and resistance to biofouling are required.
  • Aerospace and Automotive:
    • Engine Components: Use in high-wear environments where DLC is traditionally applied, with the added benefit of preventing microbial growth in fuel or fluid systems.
View Original Abstract

Abstract In the present work, DLC coatings, well known for their antiwear properties, were modified by introducing to the structure an additive metal with antibacterial properties—silver. Diamond-like coatings doped with silver were deposited on Cr-CrN layers created on steel 316L. To create the coatings, high-power impulse magnetron sputtering (HiPIMS) was used. The work carried out was divided into doping of DLC layers with silver and obtaining coatings with different contents of this metal by modifying the frequency of the voltage pulses applied to the silver target magnetron and investigating of the surface morphology, chemical and phase composition, mechanical properties and antibacterial activity. Light microscopy was used to analyse the surface morphology. The mechanical properties of the coatings were investigated using nanoindentation and the scratch method. Analysis of the antibacterial properties was carried out using two bacterial strains: Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The results showed that silver-doped DLC at a magnetron pulse frequency of 200 Hz had the best mechanical properties compared to other silver-doped coatings and possessed bactericidal activity.