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RMS Foundation 2544 Bettlach
Implant Testing and Failure Analysis
Lukas Eschbach
27th June 2013
BioTiNet Workshop 2013 S13_0001
Overview
Introduction to titanium implants
7 questions related to implant testing and failure analysis:
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
2
Bone plates and screwsCups / backingsCoatingsContourable implants
Titanium: Application as bone implants
3
IM nailsPre-shaped bone platesScrewsSpinal implantsNon-cemented hip stems
Titanium Alloys: Application as bone implants
4
Titanium: History
• 1795: Existence of Titanium suspected because of periodic table of the elements
• 1825: Titanium was detected• 1925: Reduction to the pure titanium metal• 1946: Industrial production of titanium• 1965: AO ASIF introduced DC Plates in Titanium• Today: Titanium is widely used in chemical industry, in aerospace and
medicine
5
Implant Testing
• Chemical composition: Main elements*, trace elements*• Microstructure*• Hardness• Static mechanical tests: Tensile*, bend test*, torsional test• Surface properties: Roughness• Fatigue• Wear• Corrosion• Biocompatibility• Cleanliness
* Requirements in ISO 5832 Standard
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RMS Foundation 2544 Bettlach
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100 µµµµm100 µµµµm
Commercial pure titaniumISO 5832-2
� α (T < 882°C) hexagonal close packed
� β (882°C < T < 1670°C) body centered cubic
� fine grained, single phase structure� grain size shall not be coarser than no. 5
according to ASTM E1127
TiCP – Chemical Composition
Grade 1 Grade 2 Grade 3 Grade 4
N (max.) 0.03 0.03 0.05 0.05
C (max.) 0.10 0.10 0.10 0.10
H (max.) 0.0125 0.0125 0.0125 0.0125
Fe (max.) 0.15 0.20 0.25 0.30
O (max.) 0.18 0.25 0.35 0.45
Ti Rest Rest Rest Rest
According to ISO 5832-2
CP titanium is classified into different Grades according to the levelof impurities (Fe and O). The different Grades also have different strength levels.
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Combustion analysis
Bruker G8 Galileo
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Combustion analysis of O, N, H, and C/S
• Oxygen:Melting at up to 2700 °C under He (inert carrier gas)Redox-Reaction to COIR-Detection
• Hydrogen:Melting at up to 2100 °C under N2 (inert carrier gas)Detection of the change in the thermal conductivity
• Nitrogen:Melting at up to 2700 °C under He (inert carrier gas)Detection of the change in the thermal conductivity
• Carbon and Sulfur:Melting at up to 1300 °C in reactive gas (oxygen, class 48) Detection of CO2 und SO2 by selective IR-Detection
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Combustion analysis of O, N, and H
• Oxygen, nitrogen and hydrogen in solids, such as steel, non-ferrous metals, aluminium, titanium, zirconium, P/M materials, ores, ceramics, glass etc.
Range of measurement:Oxygen 0.1 to 250 µg/g (ppm)
200 µg/g (ppm) to 0.5% (2 ranges)
Nitrogen 0.1 µg/g (ppm) to 0.5%
Hydrogen 0.01 to 1000 µg/g (ppm)
Enlargement of the range by reduction of specimen size
• Limit of detection:O, N, H 0.01 µg/g
• O, N, H calibrationWith standard specimens, certified reference materials or the integrated gas calibration unit using a reference gas
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O and N in CP Titanium
Influence of oxygen (solid lines) and nitrogen (dashed lines) on the mechanical Properties of titanium at ambient temperature [Zwicker]
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RMS Foundation 2544 Bettlach
Cold Deformation of CP Titanium
Influence of cold deformation by drawing on the mechanical properties of CP titanium [Zwicker]
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TiCP – Mechanical Properties
Grade Condition Yield strength Tensile strength Elongation
1 AN 170 MPa 240 MPa 24%
2 AN 275 MPa 345 MPa 20%
3 AN 380 MPa 450 MPa 18%
4A AN 483 MPa 550 MPa 15%
4B CD 520 MPa 680 MPa 10%
Condition: AN = Annealed; CD = Cold Deformed
Acc. ISO 5832-2:1999; minimum values
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αααα- and ββββ-stabilizing Elements
a) α-stabilizing elements: Al, O, N, C
b) β-stabilizing elements: Mo, V, W, Nb
c) in Ti nearly unsoluble Elements: Cu, Mn, Cr, Fe, Ni(eutectoid forming elements)
Neutral Elements: Zr, Sn, ...
a) b) c)
15
25 µµµµm
Ti-6Al-7Nb alloyISO 5832-11
the microstructure of TAN and TAV consists of a mixture of α- and β-grainsit is standardized in ISO 20160
the microstructure shall meet ratings A1 to A916
Implants for surgery - Metallic materials -Classification of microstructures for alpha+beta titanium alloy bars
Microstructure: ETTC-2 / ISO 20160 Standards
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Titanium as implant material
Advantagesvery good biocompatibility
good bone ingrowth (non-cementedsystems)
high corrosion-resistance (passive film)
Low stiffness (stress shielding)
Low density
MR compatibility
suitable as coating material
Disadvantageslimited mechanical strength
not very good for articulations
depending from design and surfaceroughness, not suitable for cementedsystems
relatively expensive
Good bone ingrowth
Bending properties
Stainless steel is often sufficient
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RMS Foundation 2544 Bettlach
7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
19
Advantage: Tailored Surface
Different surface roughness according to application
Sand blasted Rough alumina Etched + Polished +
and acid etched blasted anodized anodized
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Advantage: Tailored Surface
21
Old bone
Bony Integration of Ti Implants
Integration can be an advantage or a disadvantage (Implant removal)
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Advantage: MRI Compatibility
Ti implants cause clearly less artifacts during magnetic resonance imagingcompared to stainless steel
MR image without Schanz screw Schanz screwimplant CP titanium implant stainless steel
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CP Titanium: Coating Applications
Plasma Spray (Div.)
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RMS Foundation 2544 Bettlach
CP Titanium: Coating Applications
Plasma Spray
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CP Titanium: Coating Applications
Beads (Cups, knees, shoulders, …)
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CP Titanium: Coating Applications
Sintered porous structures (Div.)Wires, mesh (Cups, stems)
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CP Titanium: Coating Applications
Powder (RM Cup)
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Titanium: Coating Applications
Electrochemical treatment
Modified chemical composition
Modified topography
Surface treatment by means of APC (SEM image)
uncoated
APC coatedCage for spinal surgery
(Patent EP 1372749)
CP Titanium: Coating Applications
PVD (Finger, Physiologic Hip)
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RMS Foundation 2544 Bettlach
Torsional Properties of Bone Screws
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7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
32
Anodic Oxidation: Color Coding
• No painting, no coating• Electrochemical growth of oxide layer to a defined thickness = „anodizing“• 6+ different colors possible• Cleaning, washing, sterilization,
contamination can modify color
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Interference Colors
Color is depending on thickness of oxide layer (extinction of a specific wavelength)
Oxide layer
Titanium
Extinction of a wavelengththrough destructiveinterference
Visible light emission
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Electrochemical Anodization
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Example: Discoloration of a midface plate
Discoloration of anodized midface H-Plates during sterilization (steam/autoclave)
Gold may turn to redred may turn to gold
Possible reasons
Change in oxide layer thickness?Contamination of the surface?
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RMS Foundation 2544 Bettlach
XPS: Sputtering and Data Acquisition
Sputtering withArgon-Ions
XPS-Analysis of the sputtered surface
X-ray irradiation
Chemical information from „inside“ the specimen for
• Reference measurement (bulk material)
• Depth profile (Oxide layer, Coatings, Carburization, …)
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XPS survey spectrum
Survey spectrum H plate
1200 1000 800 600 400 200 00
50000
100000
150000
200000
250000
TiAuger
O
N
Inte
nsity
[Cps
]
Binding energy [eV]
C
Ti
OAuger200 150 100 50 00
5000
10000
15000
20000
O
Ti
Ti
AlSiSiAl
P
S
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XPS sputtering
Depth profile of the golden anodisation: Layer compositionLayer thickness
Layer thickness gold: ca. 110 nm (Sputterrate: 5 nm/min)
Layer thickness red: ca. 120 nm
Dat a acquired on a Kratos Axis Nova at RM S foundation and processed with CasaXPS.
x 104
0
10
20
30
CP
S
470 466 462 458 454 450Binding Energy (eV)
Binding energy [eV]
Ti ox
Ti met
sputtering
0 5 10 15 20 25 30 350
10
20
30
40
50
60
70
Ti met Ti ox O C N Al
Con
cent
ratio
n [a
t%]
Sputter time [min]- Al present after
sputtering
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SEM & EDX
Particles present even after sputtering
Al
Ti
Ti
Ti
Ti
Al Particleson Ti Matrix
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Summary
No relevant contamination, foreign elements not responsible for discolorationAluminium and silicon dioxide particles on the surface, but not responsible for discolorationMinor changes in the oxide layer thickness cause the colour shift from gold to red � minor oxidation or layer abrasion can lead to
discolorations
Corrective actions:Choose a slightly lower voltage for gold anodization and a slightly higher voltage for red anodization
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7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
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RMS Foundation 2544 Bettlach
Titanium Allergies?
Nickel, chromium, and cobalt are known allergenes. Titanium is mostly judged asnon-critical, but:P. Thomas et al: Gibt es Titanunverträglichkeit? Biomaterialien 3 (2), 2002, p.90
0.1
1
10
100
Jan 00 May 00 Sep 00 Nov 00
Retrieval
Stim
ula
tion
In
dex
Titanium Reactivity, TiO2 10-4M, in vitro
0.1
1
10
100
Jan 00 May 00 Sep 00 Nov 00
Retrieval
Stim
ula
tion
In
dex
Titanium Reactivity, TiO2 10-4M, in vitro
0.1
1
10
100
Jan 00 May 00 Sep 00 Nov 00
Retrieval
Stim
ula
tion
In
dex
Titanium Reactivity, TiO2 10-4M, in vitro
In vitro Lymphocyte
reaction to titanium
(proliferation test)
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Metal Allergies Related to Implants
• Other possible influences• Wear debris from instruments: Drill bits, Sleeves (hardened steel)• Drugs• Impurities / residues from implant production (blasting media, copper)
• Explants should be available for investigation• Check for chemical composition• Check for cleanlines
44
7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
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Do titanium implants corrode?
46
Corrosion of Surgical Instruments
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Corrosion resistance
� titanium is very reactive...
...in the presence of oxygen (in water, air and phy siologic solutions) the surface reacts...
� ... a stable, dense, about 3 nm thin oxide layer is formed (passive layer)
This titanium oxide layer is responsible for the ou tstanding corrosion resistance of titanium in physiologic solutions
What happens it this layer is destroyed locally (e. g. by scraching with a surgical instrument)?
� No negative effect, because the layer is rebuilt spontaneously and immediately
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RMS Foundation 2544 Bettlach
Methods: Electrochemistry by EC-Pen
Labview
control-unit
Potentiostat
ec-pen
-0.2 0.0 0.2 0.4 0.61E-3
0.01
0.1
1
10
100
1000
µA/c
m2
V (SCE)
Example for pitting corrosion
Corrosive break-throughof the passive layer (pitting)
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Pitting Corrosion
Ti-6Al-7Nb alloy: Potentiondynamic testing
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.21E-4
1E-3
0.01
0.1
1
10
100
1000
anodized and passivated anodized
µA/c
m2
V (SCE)
50
Crevice Corrosion
• Definiton Crevice Corrosion:Localized corrosion of a metal surface at, or immediately adjacent to an area that is shielded from full exposure to the environment because of close proximity between the metal and the surface of another material
www.corrosionsource.com
• Crevices are critical because of …• Local differences in O2 concentration (repassivation ability)• Local differences in pH (Hydrolysis → pH decrease)• Local differences in Cl- concentration
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Crevice Corrosion
Broken 11.0 mm Femoral nail, Implant Steel ISO 5832 -1with traces of corrosion
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Crevice Corrosion: Stainless Steel
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Crevice Corrosion: Titanium Implants (TiCP)
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RMS Foundation 2544 Bettlach
Conclusions Crevice Corrossion
• Most common corrosion phenomena in implants• Often found on the fatigue fracture surfaces of broken Stainless
Steel implants, less often on broken titanium implants
• Modular systems (multi component) with crevices are critical
• Combination with laser marking in the crevice should be avoided
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7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
56
Galvanic Corrosion: Definitions
• Galvanic corrosion is an electrochemical process in which one metal corrodes preferentially when in electrical contact with a different type of metal and both metals are immersed in an electrolyte
• Corrosion associated with the current of a galvanic cell consisting oftwo dissimilar conductors in an electrolyte
www.vacaero.com
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• Difference in electrochemical potential• Surface area ratio• Passive layer
Material combinations in implant systems
+
+
= ?
= ?58
Studies on Galvanic Corrosion of Implants
• In vitro Studies (Corrosion Tests)• In vivo Studies (Case Studies)• Large prospective / retrospective Studies
• Generally accepted: All combinations of Co-base and Ti-base implant alloys
• Debated: All combinations of implant Stainless Steel with Co-base and Ti-base alloys
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Griffin CD et al. J Biomed Mater Res 1983;17-3:489-500
• Most of the articles arguing against the mixing of dissimilar alloys in implant systems rely on just one in vitro study by Griffin et al.
• Surprisingly, this publication comes to the conclusion that mixing of 316L implant steel to Co- or Ti-based alloys is not recommended, although the stainless steel alone showed approximately the same corrosion resistance as the different combinations of materials.
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Griffin CD, Buchanan RA, Lemons JE.In vitro electrochemical corrosion study of coupled surgical implant materials. J Biomed Mater Res 1983;17-3:489-500.
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RMS Foundation 2544 Bettlach
Rüedi TP. Titan und Stahl in der Knochenchirurgie.Vol. Issue 123: Springer Edition, 1975
• Most important study on the question of mixing SS and Ti• Theoretical work on the mixing • Sheep study on the tissue compatibility • Clinical study with more than 500 patients• Conclusions: combination of SS and Ti react like the “less noble” partner of
the two (stainless steel)• It should be permitted to combine an elastic titanium plate with stronger
stainless steel screws• Combination of Ti plates with SS screws did not show any clinical or
radiographic disadvantages in more than 500 patients.
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Collier JP et al. J Bone Joint Surg [Br] 1992;74-B:5 11-7
• Study of 139 explanted modular femoral hip prostheses• Co-alloy femoral head + Ti-alloy stem results in the potential for
galvanically-accelerated crevice corrosion• Corrosions only observed in the mixed-metal prostheses (25 out of 48
cases) not in single-alloy, modular components, even after longer implantation.
• No specimens corroded after less than nine months in vivo, but all with more than 40 months
• Study clearly shows increased crevice problems in the routinely performed combination of CoCr-alloys and Ti-alloys.
Collier JP, Surprenant VA, Jensen RE, Mayor MB, Surprenant HP. Corrosion between the Components of Modular Femoral Hip Prostheses. J Bone Joint Surg [Br] 1992;74-B:511-7
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Collier JP et al. J Bone Joint Surg [Br] 1992;74-B: 511-7
63
Mixing of Metals is practiced…
• Information from clinics and surgeons: Stainless Steel and Ti implants are mixed in some cases
• Adverse effects are not known from literature• Mixing is not often performed in European and northern American countries but more
frequently in countries of southern America, Africa or Asia where stock logistics are sometimes more problematic
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Mixing of Metals is practiced…
65
• Specific case of mixing of Ti-alloy and SS screws in the same Ti-alloy bone plate operated in Austria was reported to the RMS Foundation
• Retrieval after few weeks of implantation following an implant failure not related to the mixing of materials
• Stainless steel screws showed some staining but no extensive corrosion signs. The surgical report did not mention the fact of mixing of materials.
… but not allowed
• All major orthopaedic implant manufacturer (DePuy, Biomet, Zimmer, Stryker, Smith & Nephew, Synthes) advice not to combine Ti and SS in situations of direct contact in implant systems
DePuy (Johnson & Johnson):WARNINGSMIXING METALS CAN CAUSE CORROSION. There are many forms of corrosion damage and several of these occur
on metals surgically implanted in humans. General or uniform corrosion is present on all implanted metals and alloys. The rate of corrosive attack on metal implant devices is usually very low due to the presence of passive surface films. Dissimilar metals in contact, such as titanium and stainless steel, accelerates the corrosion process of stainless steel and more rapid attack occurs. The presence of corrosion often accelerates fatigue fracture of implants. The amount of metal compounds released into the body system will also increase. Internal fixation devices, such as rods, hooks, wires, etc., which come into contact with other metal objects, must be made from like or compatible metals. Avoid coupling of stainless steel with the Surgical Titanium Mesh System implants.
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RMS Foundation 2544 Bettlach
Standard EN ISO 21534:2009
• Non-active surgical implants - Joint replacement implants - Particular requirements(ISO 21534:2007) Appendix C (Informative)
• Suitable combinations of dissimilar metals without articulation:• Co-base alloys + Ti alloys (TAN, TAV)• Dissimilar Co-base alloys• Implant Stainless Steel + Ti alloys (TAN, TAV)• Dissimilar Implant Stainless Steels• SS ISO 5832-9 + Co-base alloys
• Unsuitable combinations of dissimilar metals without articulation:• Stainless Steel ISO 5832-1 + Co-base alloys • Stainless Steel ISO 5832-1 + CP Ti
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Conclusions Galvanic Corrosion
Based on this information it can be concluded that:• Some facts indicate that today’s quality implant materials like implant stainless steel,
Co-alloys, and Ti-alloys can safely be combined in stable implant systems• The passive surface protective layer is thought to be sufficient to prevent excessive
galvanic currents in non-critical situations• Combinations will not be worse than the less noble partner in many combinations• More severe conditions (crevice, fretting or pitting) may destroy the protective layer
resulting in dissolution of the metal components accelerated by the galvanic potential difference. This is confirmed by a large study on explanted modular hip components
• When mixing SS with Ti- or Co-Alloys, it may be recommended to choose a stainless steel of higher corrosion resistance (ISO 5832-9 or better) and to absolutely avoid fretting and crevice situations (difficult in modular systems)
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7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
69
TiCP: Typical Fracture Surfaces
2008_4440.jpg
70
2008_3921.jpg
TiCP: Typical Fracture Surfaces
71
2008_4454.jpg
TiCP: Typical Fracture Surfaces
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RMS Foundation 2544 Bettlach
TiCP: Typical Fracture Surfaces
73
Bone fracture16.09.2003
Product Failure
• Patient (female), 39y, 64 kg, Ulna shaft fracture left
Op17.09.2003
Plate fracture19.12.2003
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Investigation of Plate Failure
75
Loading capacity of the femur
8500 N 8000 N500 N
8000 N500 N
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7 Questions related to testing and failure analysis
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
77
Titanium and Notch Sensitivity
Non-cemented hip stem, Ti6Al7Nb alloy with hydroxyapatite coatingHFR Hôpital Cantonal FribourgFailure of the hip stem in the neck, around 13 mm below the cone
AnamnesisMale patient, born 1941Initial implantation 20.10.2009Revision: 20.01.2011, Exchange of femoral head (instability)Date of prosthesis fracture: unknownExplantation: 22.10.2012
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RMS Foundation 2544 Bettlach
Titanium and Notch Sensitivity
Bild Nr.: 2013_06386
Overview: Received parts
Bild Nr.: 2013_06387
Detail: Fracture site
79
Titanium and Notch Sensitivity
InvestigationsMacroscopic documentationExamination of the raw material certificatesExamination of fracture surface (SEM) and material identification (EDX)Metallography
Microstructure: Transversal and longitudinalVickers hardness
80
Titanium and Notch Sensitivity
Bild Nr.: 2013_06395
Distal fracture surface with rounded edges
81
Titanium and Notch Sensitivity
Bild Nr.: 2013_06396
Overview of the proximal fracture surface (sputtered). Less damagedbut still rounded edges
82
Titanium and Notch Sensitivity
Bild Nr.: 2013_06398
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Titanium and Notch Sensitivity
Bild Nr.: 2013_00280
Bild Nr.: 2013_00282
Bild Nr.: 2013_00278
Fatigue striations Mixed fracture
Forced fracture
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RMS Foundation 2544 Bettlach
Titanium and Notch Sensitivity
EDX: Identification as TiAlNb alloy
85
Titanium and Notch Sensitivity
Bild Nr.: 2013_00795
Transversal cut: Alpha/Beta-Microstructure A4 according to ISO 20160
Average hardness HV0.5: 315.
Equivalent tensile strength: 914 MPa.
86
Titanium and Notch Sensitivity
Raw material certificate according to ISO 5832-11Numerous surface destruction sites visible macroscopically Fracture surface analysis:
Fracture initiation not localised clearly (lateral)Destruction of the surface not clearly identified Fatigue fractureRelatively large portion of forced fracture (50%)
EDX confirms TiAlNb alloyMicrostructure and hardness are according to the standard (315 HV ~ 914 MPa; ISO 5832-11: min. 900 MPa)
� No indication for a material or manufacturing defect
� Stress concentration due to surface destruction in the area of highest load provoked the formation of a crack
� Titanium is known to be highly notch sensitive
87
The End
My 7 questions related to implant testing and failure analysis:
1. What are the special features of titanium for implants?2. Where does the coloration / discoloration of titanium implants come from?3. Can titanium cause allergic reactions?4. Do titanium implants corrode?5. Is it allowed to combine titanium implants with other metals?6. How can titanium implants break?7. How notch sensitive is titanium?
Your questions?
88
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