Diamond-like Carbon Coating for Bio-medical Implant Materials

Kwang-Ryeol Lee
Future Technology Research Division Korea Institute of Science and Technology krlee@kist.re.kr http://diamond.kist.re.kr/DLC

• Dr. R. Hauert (EMPA, Switzerland)
for valuable discussion and providing me the presentation materials on this issue.

• Prof. Jeong-Ku Kim (SKKU, Korea)
for corrosion test in body fluid condition

• Prof. In-Seop Lee (Yonsei Univ., Korea)
for tribological test of DLC coated Ti alloys in body fluid

• Prof. Hyeonee Kim (SNU, Korea)
for cell attachment and hemocompatbility test

• Prof. R. Wang (UBC, Canada)
for mechanical stability test

• Mr. Sejun Park, Mr. Heon-Woong Choi and Ms. Youngjin Lee • Financial Support from Ministry of Science and Technology of Korea

Bioimplant Materials

Requirements for Bioimplants
1. 2. 3. 4. Should not cause infections Prevent uncontrolled cell growth Maintain their integrity inside the body Interact in a controllable way with the biological environment 5. Avoid formation of debris

Surface Properties

Noninflammatory • Chemical Compatibility – Corrosion Resistance • Mechanical Compatibility – Surface Hardness. Noncarcinogenic.Required Surface Properties • Biological Compatibility – Nontoxic. Wear Resistance Diamond-like Carbon : as a Strong Candidate Coating .

Introduction to DLC 2. Load Bearing Applications Hip Joints. Knee Joints. Summary and Technical Issues . Artificial Disk 4.Contents 1. Heart valves. Flow Accelerators 3. Blood Contacting Applications Stents.

sp2 and sp3 Hybridized Bonds • High Content of Hydrogen (20-60%) .Diamond-like Carbon : DLC • Amorphous Solid Carbon Film • Mixture of sp1.

DLC: A Group of Carbon Mat’l sp3 t-aC t-aC:H diamond DLC Polymer-like Graphitic graphite No film sp2 H .

2 1.26 0.1 2.42 UV-VIS-IR >1016 2000 .51 0.2 – 0.Properties of Solid Carbon Property Density (g/cm3) Atomic Number Density (Mole/cm3) Diamond 3.03 – 0.15 – 1.8 – 2.6 VIS-IR 1010 .05 2. Refractive Index Transparency Resistivity (Ω cm) 10000 0.2 Hardness (Kgf/mm2) Friction Coeff.8 Opaque 0.8000 0.6 0.3 Graphite 2.2 – 0.8 – 3.1013 500 0.4 .3 DLC 1.

Applications of DLC CD/DVD Mold VCR Head Drum Spacer Tool Form Die Hard Disk & Slider Wrist Pin Digital VCR Tape Razor Blade .

Heart valves. Flow Accelerators 3. Blood Contacting Applications Stents. Load Bearing Applications Hip Joints. Introduction to DLC 2.Contents 1. Knee Joints. Summary and Technical Issues . Artificial Disk 4.

Blood pumps etc.Surface has to prevent thrombus formation and restenosis Steps for Thrombus formation Adsorption of proteins albumin/fibrinogen ratio Increased platelet adhesion Platelet activation and aggregation Formation of a thrombus Thrombus on a mechanical heart valve (courtesy of RWTH-Aachen) . .Blood Contacting Applications • Heart valves. Stents.

2 0 Ti TiN TiC DLC silicone elastomer Jones et al.2 1 0.Protein Adsorption on DLC 1. Cui et al.6 0.4 Albumin / Fibrinogen Ratio 1. a high ratio of albumin/fibrinogen low number of adhering platelets low tendency of thrombus formation PMMA CN Albumin/fibrinogen ratio for different surfaces. . Dion et al.4 0.8 0.

Excellent Hemocompatibility On DLC Clotting Time Measurement On glass .

Excellent Hemocompatibility PC coated accelerator Blood platelets deposited on different surfaces as a function of exposure time. DLC coated accelerator .

Prevent Cr. Ni release from 316 L steel .DLC Coated Stents DIAMOND AS® Stent .Reduce thrombus formation .

Bias voltage = -800V a-C:H. Bias voltage = -400V 1600 1400 1200 Potential (mV vs SCE) 1000 800 600 400 200 0 -200 -400 -600 10 -14 10 -13 10 -12 10 -11 10 -10 10 -9 10 -8 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 10 0 10 1 Current Density (A/cm ) 2 . Bias voltage = -400V a-C:H.Potentiodynamic Polarization Substrate Si-C:H.

DLC Coated Stents .

12 ∆L/L (a) (b) (c) (d) .04 0.02 0.00 0.06 0.10 0.08 0.Evolution of Coating Failure 500 400 Force (N) 300 (b) (a) (c) (d) 200 100 0 0.

Probably it is a-C. . coated with CARBOFILM™ CARBOFILM™ made by PVD using a pyrolytic turbostratic carbon target. CarbofilmTM by Sorin Biomedica. Inc. Hemocompatibility Chrome-cobalt alloy cage. Titanium alloy coated with DLC Products under development by Cardio Carbon Company Ltd. Problems: Wear in hinges.DLC Coated Heart Valves etc.

Heart valves. Flow Accelerators 3. Load Bearing Applications Hip Joints.Contents 1. Blood Contacting Applications Stents. Artificial Disk 4. Introduction to DLC 2. Knee Joints. Summary and Technical Issues .

Biomaterials 22 (2001) 1507 . Saikko et al. leading to osteoclast cells activation resulting in bone resorption DLC shows in atmosphere a low wear and also low friction coefficients against most materials DLC slides against its own transfer layer and only DLC is worn at a very low wear rate.Load Bearing Implants Polyethylene wear debris is the main factor limiting the lifetime of the implants Aseptic loosening. whereas the softer partner surface will not be worn Polyethylene wear debris DLC coated femoral heads for low wear ? V. wear debris initiates inflammatory response..

DLC Coating on Femoral Ball Cathode RF Power .

diluted calf serum .air .dest.Adequate lubricant .1wt% NaCl in water reduction of UHMWPE wear Hip joint simulator Lubrication: . water . tribological investigations on DLC/UHMWPE require: .Adequate tribological setup .synovial fluid no change in UHMWPE wear Pin on Disk To be clinically relevant.In vitro Wear Test DLC/UHMWPE (literature overview) Hip joint simulator (Lappalainen. Finnland) Pin on Disk Lubrication: .

In vitro Test Tribological setup Pin-on-Disk setup leads to clinically non relevant results Lubrication Surface quality phospholipids.C.synovial fluid Characterize surface Texture Hip joint simulator . Med. Biol. J. 45 (2000) 372 V. Saikko. T. Scholes et al.diluted calf serum .. adsorbed on the surfaces. Fisher et al.. Phys. Ahlroos. Wear 207 (1997) 86 single scratches increase the wear rate of UHMWPE by a factor of 30-70 J. of Engineering in Medicine 209 (1995) 263 Lubrication: . strongly influences the tribological behavior and may take part in tribochemical reactions S.

/st. J.. Shi et al. 66B (2003) 410-413 B. Mater. questionable setup promising result Tiainen: 2001 ta-C/ta-C PoD / hip simulator NaCl-water 100x less than Al2O3/Al2O3 questionable lubricant promising result Ref: steel/UHMWPE: steel/steel: ceramic/ceramic: 20-60 mm3/year 1-5 mm3/year 10-2 mm3/year (wear particles) (future allergies) (can only be replaced by ceramic) R. Diamond Relat. Tiainen. Mater. 10 (2001) 153-160 . Lappalainen et al. Res.-M. Wear 255 (2003) 1015-1021 V.DLC/DLC or DLC/metal In vitro Test (only a few papers found) Lappalainen: 2003 ta-C/ta-C hip simulator bovine serum <10-4 mm3/year promising result Shi: 2003 DLC/stainless steel PoD bovine blood serum 50x less than st.. Biomed.

-wiss.5 year’s follow-up 50% of DLC/PE failed Al2O3/PE DLC/PE Retrieved DLC-head: Numerous pits revealing the metallic substrate.. Werkstofftech. severe PE wear G. u. Taeger et al. 34 (2003) 1094 .Hip Joints: in vivo Test 101 patients DLC/PE 101 patients Al2O3/PE 8. Mat.

Adhesive Wear in Body Fluid 200 ㎛ 200 ㎛ .

the Ti-alloy ball coated with DLC (carbioceram™) No medical follow-up on these products found . AISI Z5 CNMD 21 steel coated with DLC (carbioceram™) knee-joints coated with DLC (carbioceram™) Shoulder-joint.DLC Coated Artificial Joints ankle-joint.

Failure Case (Knee Joint) ”Diamond Rota Gliding” DLN/UHMWPE kneejoints have been sold (without the necessary tests and permission) by Implant Design AG in 2001.ch . www. The implanted joints showed increased wear and partial coating delamination and had to be replaced. Additionally.swissmedic. residual coating on the upper side of the implant was held responsible for the inadequate bone ingrowth. DLN (Diamond-like Nanocomposite) produced by Beckaert. Dylyn®. In July 2001 the implantation of this knee joint was forbidden by the Swiss Federal Office of Public Health (SFOPH).

• Artificial Joints Application – Needs an improved test method to obtain clinically relevant results. blood pumps are now available in the market.Summary • DLC film is not a specific materials but a group of amorhpous carbon materials • Blood Contacting Applications – Good hemocompatibility – DLC Coated stents. – DLC/DLC or DLC/metal combinations show more promising results than other combinations. . heart valves.

because the DLC film is not a specific material.Technical Issues • Careful consideration on the DLC film itself is required. • Stents – Stability of the coating with respect to the plastic deformation – Interface design would be helpful to increase the reliability. • Artificial Joints – Characterization of the coating under an adequate test condition • Does it really reduce the PE debris? • Is it possible to have new design such as DLC/DLC or DLC/metal? – Stability of the coating during sliding in body fluid condition – Need tight control of the substrate surface . • Stability of DLC coating in body fluid condition is one of the most critical issues for the biomedical applications.

re.Diamond-like Carbon Coating for Bio-medical Implant Materials Kwang-Ryeol Lee Future Technology Research Division Korea Institute of Science and Technology krlee@kist.re.kr http://diamond.kr/DLC .kist.

osteoblasts etc. Eng. Jones. Lu. ML-1 cells.no cytotoxicity DLC may be expected to be biocompatible in vivo. ) .good viability .no cellular damage .W.good growth rate .Cells in contact with DLC Many in vitro experiments with different cell types (macrophages. Bio-Med. Cell viability on control and DLC-coated plastic dished for ML-1 cells [L. Wu.L. R. human embryo kidney 293 cells.no morphological changes .no inflammatory reactions . fibroblasts. M. 3 (1993) 223]. .C. Mater.

15 60000 ALP Activity 0.20 Differentiation Cell Number [/cm2] 80000 0.Cell Growth Behavior (HOS: Human Osteo-sarcoma) Proliferation 100000 0.05 20000 0 0.10 40000 0.00 Thermanox DLC si-DLC Thermanox DLC si-DLC 3 days 10 days .

4 kD Plasma Glas Ti 23 13 7 0 Tunable protein adsorption between Ti and DLC by the Ti concentration in Ti-DLC.8 kD 37.3 kD 61. Molecular weight marker is indicated on the left side. at% Ti Adsorption of human plasma proteins on a-C:H/Ti Chromatographic analysis of the proteins. a-C:H.5 kD 50.6 kD 25. .Protein adsorption on Ti-DLC Molecular weight 184 kD 115 kD 86.

4% V a-C:H/15% V after 10 days in vitro .BMC on V-DLC 300 µm Tunable poisoning: a-C:H/3% V a-C:H Poisoning of the BMC cells due to vanadium dissolution out of the V-DLC film a-C:H/7.

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