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Biomimetic Diamond-like Carbon Coating on a Lumen of Small-diameter Long-sized Tube Modified Surface Uniformly with Carboxyl Group using Oxygen Plasma

MetadataDetails
Publication Date2022-12-16
JournalJournal of Photopolymer Science and Technology
AuthorsYuichi Imai, Hiroyuki Fukue, Tatsuyuki Nakatani, Shinsuke Kunitsugu, Kazuhiro Kanda
InstitutionsUniversity of Hyogo, Okayama Medical Center
Citations4
AnalysisFull AI Review Included

Technical Documentation & Analysis: Biomimetic DLC for Medical Applications

Section titled “Technical Documentation & Analysis: Biomimetic DLC for Medical Applications”

This research successfully demonstrates a novel method for creating biomimetic, anti-biofilm surfaces on small-diameter medical tubing using functionalized Diamond-like Carbon (DLC). This achievement leverages advanced plasma Chemical Vapor Deposition (CVD) techniques, aligning closely with 6CCVD’s core expertise in engineered carbon materials.

  • Application Focus: Prevention of bacterial adhesion and biofilm formation in small-diameter medical tubes, such as urinary catheters (1-2 mm inner diameter).
  • Methodology: AC high-voltage burst plasma CVD was used to deposit hydrogenated amorphous carbon (a-C:H) DLC onto the lumen of silicone tubes, achieving an aspect ratio of 750 (1500 mm length / 2 mm ID).
  • Functionalization: Subsequent short-duration oxygen plasma treatment (1-5 s) successfully introduced hydrophilic carboxyl groups (O-C=O, C-O bonds).
  • Biomimetic Success: The functionalization shifted the surface zeta potential from positive (plain DLC) to a highly negative charge (-15.9 mV), mimicking natural biocompatible surfaces.
  • Material Properties: The resulting DLC film was intentionally soft (Hardness: 0.79 GPa; Reduced Elastic Modulus: 8.51 GPa), ensuring flexibility and preventing delamination on soft resin substrates.
  • Performance: The functionalized DLC significantly inhibited Pseudomonas aeruginosa adhesion and reduced total biofilm biomass and thickness compared to plain DLC and uncoated control samples.

The following hard data points were extracted from the structural and performance analysis of the DLC films:

ParameterValueUnitContext
Tube Inner Diameter (ID)1 - 2mmTypical catheter size
Tube Length (Max Glow Discharge)1500mmAchieved overall length in silicon tube
Aspect Ratio (Length/ID)750N/AAchieved for 2 mm ID tube
DLC Deposition Time20minStandard deposition duration
Oxygen Plasma Treatment Time1 - 5sOptimized for functionalization
AC Voltage (Discharge)5kVHigh-voltage plasma CVD parameter
Offset Voltage2kVHigh-voltage plasma CVD parameter
Combined Pressure (CH₄ + O₂)39PaPlasma processing environment
sp³ / (sp³ + sp²) Carbon Ratio43.9%Determined by NEXAFS analysis (a-C:H classification)
Hardness (HIT)0.79GPaMeasured via nanoindentation (Soft, polymer-like DLC)
Reduced Elastic Modulus (Er)8.51GPaMeasured via nanoindentation (Flexible film)
Minimum Zeta Potential-15.9mVAchieved after 1 s O₂ plasma treatment
Carboxyl Bond Ratio (O-C=O)5.38%Increased from 1.13% (plain DLC) after O₂ plasma
Biofilm Thickness Reduction (vs. Control)P < 0.01N/ASignificant reduction achieved at 1 s O₂ plasma

The experiment relied on specialized plasma CVD and post-treatment techniques to achieve uniform coating and functionalization on high-aspect-ratio lumens.

  1. Equipment Setup: Utilized a custom AC high-voltage methane plasma-CVD system designed for coating the inner surface of long, small-diameter tubes.
  2. Source Gases: Methane (CH₄) was used as the carbon source for DLC deposition. Oxygen (O₂) and Ammonia (NH₃) were introduced for surface modification/functionalization. Argon (Ar) was used as a carrier/diluent gas.
  3. DLC Deposition Parameters: The plasma was generated using 5 kV AC voltage, 2 kV offset voltage, 10 kHz frequency, and 10 pps pulse frequency, maintaining a combined pressure of 39 Pa. DLC deposition time was 20 minutes.
  4. Surface Functionalization: An AC high-voltage burst oxygen plasma process was applied immediately after DLC deposition for short durations (1-5 seconds) to introduce carboxyl (O-C=O) and hydroxyl (C-O) functional groups.
  5. Structural Analysis: NEXAFS (Carbon K-edge), RBS/ERDA (Hydrogen content, Areal Density), and Nanoindentation (Hardness, Elastic Modulus) were used to classify the a-C:H film structure (43.9% spÂł ratio).
  6. Surface Chemistry Analysis: XPS (X-ray Photoelectron Spectroscopy) was used to confirm the increase in C-O and O-C=O bonds, and Zeta Potential measurements confirmed the shift to a negative surface charge.
  7. In Vitro Evaluation: Anti-adhesion and anti-biofilm properties were tested using GFP-labeled Pseudomonas aeruginosa strains in a continuous-flow artificial urine system over 72 hours.

The research highlights the critical role of advanced CVD technology and precise surface engineering in developing high-performance biomaterials. While this paper focuses on DLC, 6CCVD is the global leader in high-purity, crystalline CVD diamond, offering superior mechanical, thermal, and electrochemical properties essential for next-generation medical and sensor applications.

For researchers seeking to transition from amorphous DLC to high-performance crystalline diamond for rigid medical components, high-wear parts, or advanced sensing elements, 6CCVD recommends:

  • Optical Grade Single Crystal Diamond (SCD): For applications requiring ultra-smooth surfaces (Ra < 1nm) and high purity, ideal for optical windows, high-precision tools, or rigid sensor components where biocompatibility and low friction are paramount.
  • Polycrystalline Diamond (PCD): Offers exceptional hardness and wear resistance, suitable for high-durability medical tooling or implants. 6CCVD can supply PCD plates up to 125 mm in diameter.
  • Heavy Boron-Doped Diamond (BDD): Highly relevant for biomimetic and electrochemical applications. BDD surfaces can be functionalized (e.g., with oxygen plasma) to control zeta potential and surface charge, offering stable, highly conductive, and biocompatible platforms for biosensors or active anti-fouling surfaces.

6CCVD’s manufacturing capabilities directly address the need for highly customized, engineered carbon surfaces, extending beyond the limitations of the DLC films described:

Research Requirement6CCVD CapabilityTechnical Advantage
Custom DimensionsPlates/wafers up to 125 mm (PCD); Substrates up to 10 mm thick.Provides large-area, rigid diamond platforms for advanced medical devices and sensors, complementing flexible tube coatings.
Surface FunctionalizationIn-house plasma treatment and chemical modification expertise.We can replicate or extend the oxygen plasma functionalization technique to BDD and SCD surfaces to control zeta potential and enhance protein adsorption characteristics.
MetalizationInternal capability for Au, Pt, Pd, Ti, W, Cu deposition.If the research requires integrated electrodes (e.g., Ti/Pt/Au used in related studies) or bonding layers, 6CCVD provides precise, custom metalization services.
Surface FinishUltra-low roughness polishing: Ra < 1nm (SCD) and Ra < 5nm (Inch-size PCD).Essential for minimizing bacterial adhesion and improving flow dynamics in medical devices, surpassing the roughness limitations often associated with DLC.
Global LogisticsGlobal shipping (DDU default, DDP available).Ensures rapid and reliable delivery of custom engineered diamond materials worldwide.

The successful development of biomimetic DLC requires deep knowledge of plasma chemistry, surface physics, and material structure (sp³/sp² ratios, hydrogen content). 6CCVD’s in-house PhD team specializes in optimizing CVD growth parameters and post-processing techniques to meet stringent performance requirements. We offer consultation for projects requiring:

  • Material Selection: Guidance on selecting the optimal diamond type (SCD, PCD, BDD) for specific anti-biofilm or biosensing applications.
  • Surface Engineering: Assistance in designing custom functionalization recipes to achieve target zeta potentials, hydrophilicity, and protein adsorption profiles.

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

View Original Abstract

Silicone tubing is used in small-diameter long-sized tubes for medical applications, such as urinary catheters. However, bacteria in urine adhere to the catheters, forming colonies and biofilms and resulting in blockages and urinary tract infections. Therefore, we have reported a method of AC high-voltage plasma chemical vapor deposition to prevent bacterial adhesion by depositing diamond-like carbon (DLC) on a lumen of a silicone catheter and smoothing the surface. However, the sp3/sp2 structure of DLC on the lumen surface is unresolved, and biomimetic DLC with a functionalized surface has not been investigated. Therefore, we analyzed a flexible membrane structure that can deform as the resin tube deforms. In addition, we developed a lumen surface-modification method using an AC high-voltage burst oxygen plasma processing to bring the DLC surface closer to the in vivo environment. We succeeded in creating biomimetic DLC and introducing carboxyl groups. Using this technology, the surface functionalization of medical tube materials is biocompatible with various protein-adsorption properties.