Surface Treatment of Titanium - KKS Ultraschall AG
Surface Treatment of Titanium - KKS Ultraschall AG
Surface Treatment of Titanium - KKS Ultraschall AG
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<strong>Surface</strong> <strong>Treatment</strong> <strong>of</strong> <strong>Titanium</strong><br />
Christiane Jung<br />
<strong>KKS</strong> <strong>Ultraschall</strong> <strong>AG</strong>, Steinen SZ<br />
The Tribology <strong>of</strong> Precision<br />
Swiss Tribology Meeting<br />
SBB Centre Löwenberg in Murten, Switzerland<br />
16. November 2007<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Outline:<br />
1. <strong>KKS</strong> <strong>Ultraschall</strong> <strong>AG</strong><br />
2. <strong>Surface</strong> <strong>Treatment</strong> <strong>of</strong> <strong>Titanium</strong><br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Pr<strong>of</strong>ile<br />
<strong>KKS</strong>-<strong>Ultraschall</strong> <strong>AG</strong><br />
Ultrasonic & <strong>Surface</strong> Technologies<br />
- Development and Production <strong>of</strong> Cleaning Units<br />
based on Ultrasonic Technology.<br />
- <strong>Surface</strong> Finish and Cleaning <strong>of</strong> Metal Parts,<br />
in particular <strong>of</strong> Implants made from <strong>Titanium</strong> and Stainless Steel.<br />
History<br />
1982: Foundation <strong>of</strong> the Company <strong>KKS</strong> Keller H.P.<br />
1999: Change to an „Aktiengesellschaft“<br />
→ <strong>KKS</strong> <strong>Ultraschall</strong> <strong>AG</strong> – <strong>Ultraschall</strong> & Oberflächentechnik<br />
2006: New Building – “Medical <strong>Surface</strong> Center”<br />
2007: 25 Anniversary<br />
Coworkers: ~ 55 (2007)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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2006<br />
2005<br />
Medical <strong>Surface</strong> Center<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Small Ultrasonic Bath, 40-95 Liter<br />
Ultrasonic Vibrators<br />
Ultrasonic Generators<br />
Products<br />
Units for <strong>Surface</strong> <strong>Treatment</strong> and Cleaning<br />
Dry-Blasting Units<br />
One-Chamber Ultrasonic Unit<br />
(Cleaning, Rinsing, Drying)<br />
Unit for Electropolishing<br />
Automated Cleaning Unit<br />
(Cleaning, Rinsing, Passivation, Drying)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Services<br />
<strong>Titanium</strong><br />
Stainless steel<br />
Metals<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Medical <strong>Surface</strong> Center<br />
<strong>Surface</strong> <strong>Treatment</strong> <strong>of</strong> Implants and Instruments made from <strong>Titanium</strong> and <strong>Titanium</strong> Alloys<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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<strong>Titanium</strong><br />
<strong>Surface</strong> properties are important !<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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The PDF-Effect <strong>of</strong> the <strong>Surface</strong><br />
„<strong>Surface</strong> <strong>Treatment</strong>“<br />
1. Protective effect (P)<br />
- chemical resistance; friction; wear; hardness; ….<br />
2. Decorative effect (D)<br />
- color; brightness; haptic ….<br />
3. Functional effect (F)<br />
- improvement <strong>of</strong> the interaction with other materials<br />
(i.e. metals, polymers, biological tissues, bone …)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Outline:<br />
2. <strong>Surface</strong> <strong>Treatment</strong> <strong>of</strong> <strong>Titanium</strong><br />
2.1. Passive Layer<br />
2.2. Color-Anodizing (<strong>KKS</strong>01, TioCol)<br />
2.3. Importance <strong>of</strong> Mechanical Pretreatment (<strong>KKS</strong>00)<br />
for the Quality <strong>of</strong> Color-Anodized <strong>Surface</strong>s<br />
2.4. Dark-Anodizing (<strong>KKS</strong>02, TioDark)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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2.1.1. The natural passive layer<br />
<strong>Titanium</strong> + Oxygen ⇒ <strong>Titanium</strong> dioxide (natural oxidation)<br />
[ Ti ] + [ O 2 ] ⇒ [ TiO 2 ]<br />
<strong>Titanium</strong> dioxide passive layer<br />
(TiO 2 )<br />
(~ 5 nm thickness)<br />
titanium substrate<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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natural passive layer<br />
Chemical Oxidation<br />
titanium substrate<br />
Oxidizing agents such as:<br />
Nitric acid (HNO 3 )<br />
Hydrogen peroxide (H 2 O 2 )<br />
Thickness < 40 nm<br />
2.1.2. The artificial passive layer<br />
Thermal Oxidation<br />
artificial passive layer<br />
titanium substrate<br />
Electrochemical Oxidation<br />
(„Anodizing“)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Decorative Effect<br />
Color-Anodizing<br />
“TioCol”<br />
2.1.3. Electrochemical Oxidation („Anodizing“)<br />
Protective Effect<br />
Thicker passive layer (up to ~ 300 nm)<br />
Protection against further corrosion.<br />
Functional Effect<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Electrochemical cell<br />
2.2. Color-Anodizing (<strong>KKS</strong>01, TioCol) start<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Electrochemical cell<br />
2.2. Color-Anodizing (<strong>KKS</strong>01, TioCol) step 1<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Electrochemical cell<br />
2.2. Color-Anodizing (<strong>KKS</strong>01, TioCol) step 2<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Increase <strong>of</strong> layer thickness changes the color<br />
due to light ray interference.<br />
Gasoline on water<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Colors are used as codes for implants and tools.<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Medical <strong>Surface</strong> Center<br />
Electrochemical Cells<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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2.4. Importance <strong>of</strong> mechanical pretreatment ( <strong>KKS</strong>00 )<br />
for the quality <strong>of</strong> color-anodized surfaces<br />
grinding media<br />
High brightness <strong>of</strong> the surfaces<br />
<strong>Surface</strong> roughness<br />
R a ~0.045 - 0.100 µm<br />
Side-view topography<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Microcrystals acting as grinding and polishing particles ?<br />
microscopic images; magnification 500<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Pretreatment with small-sized granulate<br />
combines mechanical with chemical treatment ?<br />
pH ~ 5<br />
Granulate<br />
Magnification 63<br />
impregnated with wax,<br />
plant and mineral oils,<br />
fatty acids, emulsifier,<br />
and oxides as grinding<br />
particles<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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efore anodizing<br />
sR a = 0.047 µm<br />
<strong>Surface</strong> Roughness <strong>of</strong> <strong>Titanium</strong> Discs<br />
(polished with granulate)<br />
Ti 6Al 7Nb<br />
color-anodized at 62 V<br />
sR a = 0.045 µm<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Electrochemical cell<br />
2.4. Dark-Anodizing (<strong>KKS</strong>02, TioDark)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Main steps for Dark-Anodizing (<strong>KKS</strong>02, TioDark)<br />
Start Color formation Oxygen evolution<br />
Sparking<br />
Porous outermost layer<br />
Conversion layer<br />
<strong>Titanium</strong> substrate<br />
Increasing voltage<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Raster Electron Microscopic Picture<br />
(cpTi, grade 2)<br />
before<br />
anodizing<br />
Porous outermost layer<br />
Conversion layer<br />
<strong>Titanium</strong> substrate<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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efore<br />
after<br />
Examples for dark-anodized titanium surfaces<br />
( TioDark )<br />
(Ti 6Al 4V, porous layer removed)<br />
before after<br />
before<br />
after<br />
before<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
after<br />
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<strong>Surface</strong> Topography <strong>of</strong> untreated and dark-anodized Ti 6 Al 4 V - samples<br />
before<br />
after<br />
before after<br />
sRa = 0.241 µm sRa = 0.327 µm<br />
<strong>Surface</strong> roughness for different samples <strong>of</strong><br />
cpTi (grade 2 & 4), Ti6Al4V, Ti6Al7Nb)<br />
sR a ~ 0.24 – 0.40 µm<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Suggested assignment:<br />
Contributions <strong>of</strong>:<br />
<strong>Surface</strong> characterization by Raman spectroscopy<br />
Rutile TiO 2<br />
Anatase TiO 2<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Ti 6Al 4V<br />
Scratch spots:<br />
Magnification: 63<br />
Scratch test<br />
dark-anodized sample scratches color-anodized sample<br />
(Ti 6Al 4V / Ti 6Al 4V - pair)<br />
<strong>Surface</strong> <strong>of</strong> dark-anodized sample<br />
Magnification 63<br />
expected color<br />
in scratch spot<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Diamond cone 90°; velocity: 0.1 mm/s; distance: 5 mm;<br />
zero load: 1.0 mN; load: 20 mN; load cycles: 10<br />
Scratch test<br />
(diamond / cpTi grade 4 - pair)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Friction: Steel/<strong>Titanium</strong> – Pair<br />
Dependence <strong>of</strong> the friction coefficient on<br />
the sliding distance<br />
CSM: standard tribometer,<br />
„ball on disc“ method<br />
ball: steel 100Cr6<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Initial friction coefficient<br />
sliding distance = 6.7 mm, scaled to untreated surfaces<br />
CSM standard tribometer<br />
ball: steel 100Cr6, 6mm ∅, dry; linear mode, ½ amplitude: 2mm, max linear speed: 2 cm/s, normal<br />
load: 250 mN, cycles: 470, acquisition rate: 10 Hz, temperature: 25°C, atmosphere: air, huminity: 35%<br />
CSM: standard tribometer, „ball on disc“ method<br />
35<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007
CSM nano tribometer<br />
Initial friction coefficient<br />
scaled to untreated surfaces<br />
Steel/<strong>Titanium</strong> Pair<br />
Comparison: CSM nano tribometer (20 mN load) and<br />
standard tribometer (250 mN load)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Indentation pr<strong>of</strong>il<br />
Nano- and micro-hardness <strong>of</strong><br />
dark-anodized surfaces.<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Summary<br />
Lower initial friction coefficient.<br />
Increased micro- and nano-hardness.<br />
Increased layer thickness.<br />
Very good haptic.<br />
Dense, dark and low-reflective<br />
Biocompatible<br />
TioDark<br />
compared to untreated surfaces<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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<strong>Surface</strong> <strong>Treatment</strong><br />
A great challenge<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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Acknowledgement<br />
CSM (Micro- and nano-hardness; tribology studies)<br />
INNOWEP (Nano-scratch test, wear rate)<br />
CSEM (Thickness measurements)<br />
SGS Institute Fresenius (XPS depth pr<strong>of</strong>ile analysis)<br />
Fachhochschule der Nordwestschweiz (REM/EDX)<br />
Technical University Berlin, Institute for Chemistry (Raman spectroscopy)<br />
FRT Suisse <strong>AG</strong> (<strong>Surface</strong> topography analysis)<br />
Dr. Christiane Jung, Swiss Tribology Meeting, Murten, 16. November 2007<br />
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