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


orea
Bioimplant Materials

Requirements for Bioimplants


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

• Biological Compatibility
– Nontoxic, Noncarcinogenic, Noninflammatory
• Chemical Compatibility
– Corrosion Resistance
• Mechanical Compatibility
– Surface Hardness, Wear Resistance

Diamond-like Carbon :
as a Strong Candidate Coating
Contents
1. Introduction to DLC

2. Blood Contacting Applications


Stents, Heart valves, Flow Accelerators

3. Load Bearing Applications


Hip Joints, Knee Joints, Artificial Disk

4. Summary and Technical Issues


Diamond-like Carbon : DLC
• Amorphous Solid Carbon Film
• Mixture of sp1, sp2 and sp3 Hybridized Bonds
• High Content of Hydrogen (20-60%)
DLC: A Group of Carbon Mat’l

sp3 diamond

t-aC

t-aC:H

DLC

Polymer-like

Graphitic
graphite No film

sp2 H
Properties of Solid Carbon

Property Diamond DLC Graphite

Density (g/cm3) 3.51 1.8 – 3.6 2.26

Atomic Number Density (Mole/c


0.3 0.2 – 0.3 0.2
m3)

Hardness (Kgf/mm2) 10000 2000 - 8000 500

Friction Coeff. 0.05 0.03 – 0.2 0.1

Refractive Index 2.42 1.8 – 2.6 2.15 – 1.8

Transparency UV-VIS-IR VIS-IR Opaque

Resistivity (cm) >1016 1010 - 1013 0.2 – 0.4


Applications of DLC
CD/DVD Mold Form Die

VCR Head Drum

Spacer Tool

Hard Disk & Slider

Wrist Pin

Digital VCR Tape

Razor Blade
Blood Contacting Applications
• Heart valves, Stents, 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)
Protein Adsorption on DLC

1.4
a high ratio of
Jones et al.
Dion et al. albumin/fibrinogen
Albumin / Fibrinogen Ratio

1.2
Cui et al.
1

0.8 low number of


0.6
adhering platelets

0.4

0.2 low tendency of


0
thrombus formation
Ti TiN TiC DLC silicone PMMA CN
elastomer

Albumin/fibrinogen ratio for different surfaces.


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


DLC Coated Stents

DIAMOND AS® Stent

- Reduce thrombus formation

- Prevent Cr, Ni release from 316 L steel


Potentiodynamic Polarization
Substrate
Si-C:H, Bias voltage = -400V
a-C:H, Bias voltage = -800V
1600 a-C:H, Bias voltage = -400V

1400

1200
Potential (mV vs SCE)

1000

800

600

400

200

-200

-400

-600
-14 -13 -12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
2
Current Density (A/cm )
DLC Coated Stents
Evolution of Coating Failure

500

400
(c) (d)
(b)

Force (N)
300

200
(a)
100

0
0.00 0.02 0.04 0.06 0.08 0.10 0.12

L/L

(a) (b) (c) (d)


DLC Coated Heart Valves etc.
Problems: Wear in hinges, Hemocompatibility

Chrome-cobalt alloy cage,


coated with CARBOFILM™

Titanium alloy coated with DLC


CARBOFILM™ made by Products under development by
PVD using a pyrolytic turbostratic Cardio Carbon Company Ltd.
carbon target. Probably it is a-C.

CarbofilmTM by Sorin Biomedica, Inc.


Load Bearing Implants

Polyethylene wear debris is the main factor limiting the


lifetime of the implants
Aseptic loosening, wear debris initiates inflammatory response,
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, whereas the softer partner surface will
not be worn Polyethylene wear debris

DLC coated femoral heads for low wear ?

V. Saikko et al., Biomaterials 22 (2001)


1507
DLC Coating on Femoral Ball

Cathode

RF Power
In vitro Wear Test
DLC/UHMWPE (literature overview)
Hip joint simulator
(Lappalainen, Finnland)
Pin on Disk Hip joint simulator
Lubrication: Lubrication:
- air - diluted calf serum
- dest. water - synovial fluid
- 1wt% NaCl in water
reduction of no change in
UHMWPE wear UHMWPE wear

Pin on Disk
To be clinically relevant, tribological
investigations on DLC/UHMWPE require:
- Adequate tribological setup
- Adequate lubricant
In vitro Test
Tribological setup Lubrication Surface quality

Pin-on-Disk setup leads


to clinically non
relevant results
phospholipids, adsorbed on
the surfaces, strongly
influences the tribological
behavior and may take part in
tribochemical reactions
S.C. Scholes et al., Phys. Med. Biol. 45 (2000) 372 single scratches increase
V. Saikko, T. Ahlroos, Wear 207 (1997) 86
the wear rate of UHMWPE
by a factor of 30-70
J. Fisher et al., J. of Engineering in Medicine
209 (1995) 263

Lubrication:
- diluted calf serum
- synovial fluid Characterize surface
Texture

Hip joint simulator


DLC/DLC or DLC/metal
In vitro Test (only a few papers found)

Lappalainen: Shi: Tiainen:


2003 2003 2001
ta-C/ta-C DLC/stainless steel ta-C/ta-C
hip simulator PoD PoD / hip simulator
bovine serum bovine blood serum NaCl-water
<10-4 mm3/year 50x less than st./st. 100x less than Al2O3/Al2O3

promising result questionable setup questionable lubricant


promising result promising result

Ref: steel/UHMWPE: 20-60 mm3/year (wear particles)


steel/steel: 1-5 mm3/year (future allergies)
ceramic/ceramic: 10-2 mm3/year (can only be replaced by ceramic)

R. Lappalainen et al., J. Biomed. Mater. Res. 66B (2003) 410-413


B. Shi et al., Wear 255 (2003) 1015-1021
V.-M. Tiainen, Diamond Relat. Mater. 10 (2001) 153-160
Hip Joints: in vivo Test
101 patients DLC/PE
101 patients Al2O3/PE

8.5 year’s follow-up


50% of DLC/PE failed
Al2O3/PE
DLC/PE

Retrieved DLC-head: Numerous pits revealing the


metallic substrate, severe PE wear

G. Taeger et al., Mat.-wiss. u. Werkstofftech. 34 (2003) 1094


Adhesive Wear in Body Fluid

200 ㎛ 200 ㎛
DLC Coated Artificial Joints

ankle-joint, AISI Z5 CNMD 21 steel


coated with DLC (carbioceram™)

knee-joints coated with DLC


(carbioceram™)
Shoulder-joint, the Ti-alloy ball
coated with DLC (carbioceram™)

No medical follow-up on these


products found
Failure Case (Knee Joint)

”Diamond Rota Gliding” DLN/UHMWPE knee-


joints have been sold (without the necessary tests
and permission) by Implant Design AG in 2001.
Dylyn®, DLN (Diamond-like Nanocomposite)
produced by Beckaert.

The implanted joints showed increased wear and


partial coating delamination and had to be
replaced. Additionally, residual coating on the
upper side of the implant was held responsible for
the inadequate bone ingrowth.

In July 2001 the implantation of this knee joint was


forbidden by the Swiss Federal Office of Public
Health (SFOPH). www.swissmedic.ch
Summary
• DLC film is not a specific materials but a group of
amorhpous carbon materials
• Blood Contacting Applications
– Good hemocompatibility
– DLC Coated stents, heart valves, blood pumps are now
available in the market.
• Artificial Joints Application
– Needs an improved test method to obtain clinically relevant
results.
– DLC/DLC or DLC/metal combinations show more
promising results than other combinations.
Technical Issues
• Careful consideration on the DLC film itself is required, because
the DLC film is not a specific material.
• Stability of DLC coating in body fluid condition is one of the mos
t critical issues for the biomedical applications.

• 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
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
Cells in contact with DLC

Many in vitro experiments with


different cell types (macrophages,
fibroblasts, human embryo kidney 293
cells, ML-1 cells, osteoblasts etc. )

- good growth rate


- good viability
- no morphological changes
- no cellular damage
- no inflammatory reactions
- no cytotoxicity

DLC may be expected to be


biocompatible in vivo.
Cell viability on control and DLC-coated plastic
dished for ML-1 cells
[L. Lu, M.W. Jones, R.L.C. Wu, Bio-Med. Mater. Eng. 3 (1993) 223].
Cell Growth Behavior
(HOS: Human Osteo-sarcoma)

Proliferation Differentiation
100000 0.20

80000
Cell Number [/cm2]

0.15

ALP Activity
60000

0.10

40000

0.05
20000

0 0.00
Thermanox DLC si-DLC Thermanox DLC si-DLC

3 days 10 days
Protein adsorption on Ti-DLC

Molecular weight
184 kD Tunable protein
115 kD adsorption between
86.3 kD Ti and DLC by the
61.5 kD
Ti concentration in
50.8 kD Ti-DLC.
37.6 kD

25.4 kD
Plasma Glas Ti 23 13 7 0
a-C:H, at% Ti

Adsorption of human plasma proteins on a-C:H/Ti


Chromatographic analysis of the proteins. Molecular weight marker is indicated
on the left side.
BMC on V-DLC
300 µm

Tunable
poisoning:

Poisoning of the
a-C:H/3% V a-C:H
BMC cells due to
vanadium
dissolution out of
the V-DLC film

a-C:H/7.4% V a-C:H/15% V

after 10 days in vitro

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