ho-gun kim, seung-ho ahn, jung-gu kim, *se-jun park, *kwang-ryol lee, **rizhi wang
DESCRIPTION
Corrosion Resistance of Diamond-Like Carbon (DLC) Coatings on 316L Stainless Steel for Biomedical Applications. Conference of Metallurgists COM2003, August 24-27, Canada. Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang SungKyunKwan University, Korea - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/1.jpg)
Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang
SungKyunKwan University, Korea *Korea Institute of Science and Technology, Korea
** The University of British Columbia, Canada
Corrosion Resistance of Diamond-Like Carbon (DLC) Coatings on 316L Stainless Steel for
Biomedical Applications
Conference of Metallurgists COM2003, August 24-27, CanadaConference of Metallurgists COM2003, August 24-27, Canada
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 2: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/2.jpg)
● Diamond-Like Carbon (DLC)? - amorphous structure similar to diamond - hydrogenated amorphous carbon( a-C:H )
INTRODUCTION
ADVANTAGES
●High hardness, low friction●Electrical insulation
WEAK POINT
●High compressive stress → buckling●Poor adhesion
Diamond-Like Carbon (DLC)’ A&W?
The purpose of the present investigation is to evaluate the effects of bias voltage and Si incorporation on the corrosion resistance of DLC coatings in the simulated body fluid environment.
●Chemical inertness●Resistance to wear
●Operation temperature below 500oC
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 3: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/3.jpg)
DEPOSITION CONDITIONS
RFPACVD(13.56MHz)RFPACVD(13.56MHz)
BasePressure:below2.0×10BasePressure:below2.0×10-5-5TorrTorr
SiliconBufferlayer(forresidualstress)SiliconBufferlayer(forresidualstress)
SiHSiH44,10mTorr,-400V,1min.deposition,10mTorr,-400V,1min.deposition
DLCPrecursorGas:CDLCPrecursorGas:C66HH66
DepositionPressure:1.33PaDepositionPressure:1.33Pa
BiasVoltage:-400VBiasVoltage:-400V
FilmThickness:FilmThickness:1 1 ㎛㎛
Schematics of RF PACVDSchematics of RF PACVD
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 4: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/4.jpg)
Si-C:H Bias Voltage = -400V Si-C:H Bias Voltage = -400V
EXPERIMENTAL PROCEDURES
Coating structureCoating structure
Substrate
C6H6
Buffer layer Si
Coating
5-7 nm
Substrate
Coating
Buffer layer
a-C:H Bias Voltage = -800Va-C:H Bias Voltage = -800V
a-C:H Bias Voltage = -400Va-C:H Bias Voltage = -400V
Substrate
C6H6+ SiH4
Buffer layer Si
Coating 1 ㎛
5-7 nm
1 ㎛
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 5: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/5.jpg)
EXPERIMENTAL PROCEDURES
Electrochemical evaluationElectrochemical evaluation
Diamond-like carbon (DLC) coatingsDiamond-like carbon (DLC) coatings
Potentiodynamic polarization testPotentiodynamic polarization test
Electrochemical impedance Electrochemical impedance spectroscopy (EIS)spectroscopy (EIS)
Potential : -0.25 Voc~1.5 VScan rate : 0.166 mV/sec
Frequency : 10 mHz~10k HzAmplitude : 10 mV
Electrolyte : Deaerated 0.89% NaCl, 37℃,pH=7.4 (similar to human body environment)
SEMSEM Surface and corrosion features
AFMAFM Uniformity of surface
Surface analysesSurface analyses
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 6: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/6.jpg)
RESULTS AND DISCUSSION
SpecimenEcorr
(mV)
icorr
(nA/ ㎠ )
βa
(V/decade)
βc
(V/decade)
Rp
(×103 Ω ㎠ )Porosity
Substrate-
114.6249.3 0.1285 0.1868 132.7 -
Si-C:H,Biasvoltage=-400V-
111.60.06486 0.3527 0.06077 347492.9 0.00037
a-C:H, Bias voltage = -800V
-63.11
15.33 0.1211 0.1839 2070.8 0.02407
a-C:H, Bias voltage = - 400V
-40.55
103 0.5402 0.1293 440.3 0.15556
Porosity equation ( Matthews et al.)
F : Total porosity Rpm : Polarization resistance of the substrate △Ecorr : Difference of corrosion potential
between coated and uncoated specimens. Rp : Polarization resistance of the coated steels β a : Anodic Tafel slope of the substrate
Potentiodynamic polarization test
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 10-1 100 101
-600
-400
-200
0
200
400
600
800
1000
1200
1400
1600
Pot
entia
l (m
V v
s S
CE
)
Current Density (A/cm2)
Substrate Si-C:H, Bias voltage = -400V a-C:H, Bias voltage = -800V a-C:H, Bias voltage = -400V
ΔEcorr/βa
substrate)-p(coating
e)pm(substat10
R
R F
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 7: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/7.jpg)
RE : Reference electrode
WE
Rpore
CPE1CPE2Rct
Rs
RE
RESULTS AND DISCUSSION
Electrical equivalent circuit for coated metalElectrical equivalent circuit for coated metal
WE : Working electrode
Rs:SolutionresistancebetweenworkingelectrodeandreferenceelectrodeCPE1:CapacitanceofthecoatingincludingporesintheouterlayercoatingRpore:PoreresistanceresultingfromtheformationofionicconductionpathsacrossthecoatingCPE2:CapacitanceofthecoatingwithinthepitRct:Chargetransferresistanceofthesubstrate/coating
Electrochemical parametersElectrochemical parameters
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 8: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/8.jpg)
● Electrochemical parameters obtained by equivalent simulation
Exposuretime
Rs
(Ω ㎠ )
CPE1Rpore
(×103
Ω ㎠ )
CPE2Rct
(×103
Ω ㎠ )AdCcoat,
(×10-9
F/ ㎠ )
n(0-1)
Cdl
(×10-9
F/ ㎠ )
n(0-1)
120 h
Substrate 32.96 46440 1 78.9 175200 1 252.2 -
Si-C:H,(-400V)
700.7 20.8 0.9921 3.43 47.47 0.7483 2501 0.41
a-C:H, (-800V)
11.39 5.2 0.8675 81.8 508.5 0.914 1018 1.08
a-C:H, (-400V)
929.1 878.4 0.6016 92.4 714.2 1 372.5 1.70
216 h
Substrate 33.29 48210 1 73.4 174200 1 218.2 -
Si-C:H,(-400V)
4.308 27.1 0.9602 2.9 47.05 0.5329 2062 0.48
a-C:H, (-800V)
18.2 7.74 0.8884 52.5 749.4 0.8843 1292 1.69
a-C:H, (-400V)
696 899.4 0.6099 89.9 542.2 1 342 1.73
RESULTS AND DISCUSSION
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 9: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/9.jpg)
RESULTS AND DISCUSSION
Si-C:H(-400V) coating leads to the higher Rct values than a-C:H(-400V).
a-C:H(-800V)coating leads to the higher Rctvalues thana-C:H(-400V).
Charge transfer resistance (RCharge transfer resistance (Rctct))
1 24 48 72 96 120 144 168 192 216
0
2000
4000
6000
Ch
arg
e T
ran
sfe
r R
esi
sta
nce
(ko
hm
-cm
2 )
Immersion Time(h)
Substrate Si-C:H, Bias voltage = -400V a-C:H, Bias voltage = -800V a-C:H, Bias voltage = -400V
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 10: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/10.jpg)
RESULTS AND DISCUSSION
RRpo po = R = Roopopo /A /Add ( R ( Rpopo= pore resistance )= pore resistance )
RRoopopo = ρd (ρ = specific resistance, d= coating thickness) = ρd (ρ = specific resistance, d= coating thickness)
Delamination area (ADelamination area (Add))
1 24 48 72 96 120 144 168 192 216-1
0
1
2
8
10
De
lam
ina
tion
Are
a(A
d)
Immersion Time(h)
a-SiC:H, Bias voltage = -400V a-C:H, Bias voltage = -800V a-C:H, Bias voltage = -400V
Si-C:H(-400V) coating leads to the lower delamination area than a-C:H(-400V).a-C:H(-800V) coating generally leads to the lower delamination area than
a-C:H(-400V).
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 11: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/11.jpg)
RESULTS AND DISCUSSION
Deposited surfaces ( AFM )Deposited surfaces ( AFM )a-C:H(-400V)
Si-C:H(-400V)a-C:H(-800V)
RRaa = 0.2326 = 0.2326 ㎛㎛
RRaa = 0.6157 = 0.6157 ㎛㎛
RRaa = 0.0906 = 0.0906 ㎛㎛
Roughness of Si-C:H(-400V) was lower than a-C:H(-400V) according to Si incorporation. With increasing bias voltage, roughness of a-C:H(-800V) was lower than a-C:H(-400V).
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 12: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/12.jpg)
RESULTS AND DISCUSSION
Corroded surfaces (After potentiodynamic polarization test)Corroded surfaces (After potentiodynamic polarization test)
Substrate Si-C:H(-400V)
a-C:H(-800V) a-C:H(-400V)
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
![Page 13: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/13.jpg)
CONCLUSIONS
● From the potentiodynamic test, the polarization resistance value of Si-C:H(-400V) was higher than a-C:H(-400V). Also, the polarization resistance value of a-C:H(-800V) was higher than a-C:H(-400V).
● From the potentiodynamic test, porosity of Si-C:H(-400V) was lower than a-C:H(-400V). Moreover, porosity of a-C:H(-800V) was lower than a-C:H(-400V).
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
● From the EIS results, Rct value of Si-C:H(-400V) was higher than a-C:H(-400V). Furthermore, Rctvalue of a-C:H(-800V) was higher than a-C:H(-400V).
●From the EIS results, delamination area of Si-C:H(-400V) was lower than a-C:H(-400V). In addition,delamination area of a-C:H(-800V) was lower than a-C:H(-400V).These results corresponded with the potentiodynamic test.
![Page 14: Ho-Gun Kim, Seung-Ho Ahn, Jung-Gu Kim, *Se-Jun Park, *Kwang-Ryol Lee, **Rizhi Wang](https://reader030.vdocuments.net/reader030/viewer/2022032607/5681310c550346895d97462c/html5/thumbnails/14.jpg)
CONCLUSIONS
● It was shown that corrosion resistance of DLC films with Si incorporation and higher bias voltage would be improved in corrosive environment.
Applied Electrochemistry Lab. SKKUApplied Electrochemistry Lab. SKKU
● From the AFM images, the increase of bias voltage and Si incorporation improved the surface roughness of DLC coatings. These results are consistent with the porosity calculated by electrochemical method.