Effect of Surface Treatment on Surface Characteristics of 316L Stainless Steel

Guna Selvaduray1 and Steve Trigwell2

Jose State University 2NASA Kennedy Space Center
1San

Materials and Processes for Medical Devices Conference November 14~16, 2005 Boston, MA

Presentation Outline
Introduction Motivation Experimental Procedure Analytical Techniques xxx yyy zzz Conclusions future work
G. Selvaduray SJSU November 16, 2005
2

Introduction
AISI 316L Stainless Steel

Used widely in medical devices

Ni (10~14%), Cr (16~18%), Mo (2~3%) Austenitic Fracture fixation plates, screws Intramedullary nails Stents Etc Bulk properties Surface properties

Thermomechanical/processing history affects

G. Selvaduray SJSU November 16, 2005

Surfaces & Biocompatibility

Biocompatibility affected by surface characteristics

Surface chemistry Surface roughness Surface porosity Surface thermodynamics Surface charge Others ??

Critical surface tension (of solid phase)

Chemical & mechanical processing affects/changes surface characteristics

G. Selvaduray SJSU November 16, 2005
4

Previous Studies
Relatively large number of studies relating various aspects of surfaces to biocompatibility Primarily in vivo and/or in vitro tests Wide variety of testing methods for biocompatibility Detailed correlation of effect of processing on surface characteristics and subsequent effect on biocompatibility still needed
G. Selvaduray SJSU November 16, 2005
5

Objective
Investigate the effect of surface treatment on the surface characteristics and surface chemistry of NiTi, AISI 316L, Co-Cr alloys Relate to biocompatibility and corrosion behavior This work:

Effect of mechanical polishing, electropolishing and plasma treatment on surface roughness, surface chemistry and critical surface tension

G. Selvaduray SJSU November 16, 2005

Experimental Approach
Materials

AISI 316L 19 mm x 19 mm x 0.737 mm coupons Cleaned Composition verified by GCMS

Surface treatments:

Mechanical polishing (MP)

#1000 SiC paper

MP + Electropolishing (EP) MP + Plasma treatment EP + Plasma treatment

98% He, 2% O2 63% H3PO4, 15% H2SO4, 22% DI H2O

G. Selvaduray SJSU November 16, 2005

Analysis
Surface Roughness: Atomic Force Microscopy Surface Chemistry: X-ray Photoelectron Spectroscopy Depth Profile: Auger Electron Spectroscopy Critical Surface Tension: Zisman Plots

G. Selvaduray SJSU November 16, 2005

Surface Roughness - 1
MP EP EP+ Plasma 14.06 5.23 MP+ Plasma 29.83 8.82 Roughness Average () 32.15 14.66 Standard deviation () 8.03 3.60

Mechanically polished surface

G. Selvaduray SJSU November 16, 2005

Electropolished surface
9

Surface Roughness - 2
Electropolishing very effective in reducing surface roughness Electropolishing improves surface uniformity Plasma treatment had no observable effect on surface roughness

G. Selvaduray SJSU November 16, 2005

10

Counts Label O2 OH O(H2O) BE (eV) 529.97 531.64 532.72 FWHM 1.48 1.58 1.56 Height 16700.3 8283.31 2055.77 Gauss 80.0% 80.0% 80.0% Asymm Norm. Area Rel. Area 0.0% 9575.02 59.9% 10.0% 5127.35 32.1% 15.0% 1282.52 8.0% O2

26000

Mechanically polished

24000

22000

Oxygen
OH

X-ray Photoelectron Spectroscopy

20000

18000

16000

12000

10000

8000 537 Counts 52000 50000 48000 46000 535 533 531 Binding Energy, (eV) Gauss 100.0% 80.0% 80.0% 529 527 525

Label O2 OH O(H2O)

BE (eV) 530.25 531.37 532.75

FWHM 1.46 1.59 1.80

Height 7441.4 36403.4 8364.91

O(H2O)

14000

Asymm Norm. Area Rel. Area 0.0% 3856.01 11.9% 10.0% 22689 70.0% 10.0% 5880.28 18.1%

Peak-Fit Baseline: 535.80 to 527.50 eV 44000 Reduced Chi-Square: 2.479 42000 40000 38000 36000 34000 32000 30000 28000 26000 22000 20000 18000 16000 14000 12000 10000 8000 537 535 533 531 Binding Energy, (eV) 529 527 525 O(H2O) 24000

OH

Electropolished

Oxygen

O2

G. Selvaduray SJSU November 16, 2005

11

Bond Type C-C/C-H C-O

MP 72.2 15.5 5.9 5.9 0.5 59.9 32.1 8.0 13.0 67.3 19.7 9.4 9.6 59.8 17.4 3.8 1:2.10

EP 71.6 16.2 5.3 5.1 1.7 11.9 70.0 18.1 16.3 48.4 35.3 5.6 16.3 51.5 12.1 14.6 1:1.71

EP+ Plasma 74.7 14.8 3.9 3.9 2.7 27.2 59.7 13.1 11.2 68.9 19.9 5.1 4.5 76.0 10.7 3.7 1:1.82

MP+ Plasma 77.1 12.4 4.5 3.7 2.4 65.1 28.1 6.8 7.9 80.1 12.1 0.6 0.7 81.7 15.7 1.3 1:5.88
12

X-ray Photoelectron Spectroscopy

C=O COOO-C=O O=

O-H O(H2O) Cr

Cr

Cr2O3 Cr-OH Fe FeO

Fe

Fe2O3 Fe-OOH Fe Sat Cr:Fe Ratio

G. Selvaduray SJSU November 16, 2005

XPS Results - 1
Electropolishing:

O2 in oxide form O2 in hydroxide form Cr as hydroxide Fe as metallic, Fe2O3, and hydroxide Fe as FeO

G. Selvaduray SJSU November 16, 2005

13

XPS Results - 2
Cr:Fe ratio
Bulk: 1:3.63 After mechanical polishing: 1:2.10 After electropolishing: 1:1.71 Enrichment of Cr on the surface enhanced by electropolishing Effect of plasma treatment:

MP + Plasma treatment: 1:5.88 EP + Plasma treatment: 1:1.82

G. Selvaduray SJSU November 16, 2005

14

Auger Electron Spectroscopy

10000 8000

Fe

6000

~ 35
4000 2000 0 0 25 50 75 100 125 150

Cr C Ni

AES depth profile of electropolished 316L stainless steel

15

G. Selvaduray SJSU November 16, 2005

Auger Electron Spectroscopy - 2

Element O Cr Fe Ni Thickness MP 63 16 18 3 ~ 40 EP 66 20 10 3 ~ 35 EP+ Plasma 69 10 16 5 ~ 35 MP+ Plasma 70 10 18 2 ~ 75

Ni concentration on surface significantly lower than bulk concentration of 13.78% Electropolishing enhances surface Cr concentration Surface oxide layer thickness ~ same, except for MP + Plasma
G. Selvaduray SJSU November 16, 2005
16

Conclusions
AES & XPS results consistent Electropolishing enriches Cr concentration in the surface oxide layer Surface oxide layer is a combination of Fe and Cr oxides and hydroxides Surface concentration of Ni ~ 3% - much lower than bulk concentration of 13.78% Plasma treatment reduces Cr:Fe ratio; does not improve surface passivation
G. Selvaduray SJSU November 16, 2005
17