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Unalloyed Titanium.
Sixth Edition
John Disegi
Sixth Edition
November 2008
Acknowledgement
The author wishes to acknowledge the technical contributions of
Professor O. Pohler, Oberdorf, Switzerland.
Table of Contents
Introduction
Basic Metallurgy
Properties
1. Composition
2. Microstructure
1. Physical
2. Tensile
3. Fatigue
11
4. Corrosion
13
5. Biocompatibility
16
6. Surface
17
Clinical Features
18
References
19
Glossary
23
Introduction
Titanium is the ninth most abundant element and the fourth most
abundant structural metal in the earths crust. Large deposits of rutile
and ilmenite ore are located in the United States, Canada, and Australia. Titanium metal producers have access to large raw material
reserves to ensure that the material requirements of the implant,
aerospace, chemical processing, and other critical industries will be
met in the future. A comparison of mineral reserves located in the
United States indicates that titanium is much more abundant than
other strategic minerals that are used to produce stainless steel and
cobalt base implant alloys.1
100
90
80
70
60
U.S. Mineral
Reserves (%)
50
40
30
20
10
0
Cobalt
Chromium
Nickel
Titanium
The United States mines about one-third of its titanium raw material
requirement. The balance is imported mainly from Australia.2
Titanium ore is treated with chlorine gas to produce an intermediate
titanium chloride product. The titanium chloride is reduced with either
magnesium or sodium metal to produce titanium metal granules. The
resultant granules are pressed into a dense compact, and the compacts
are welded together to form an electrode for vacuum melting. An
electric current is passed through the electrode in a vacuum arc furnace
to produce a titanium ingot. The ingot is normally double or triple
vacuum arc melted to yield extremely pure and homogeneous titanium
metal. The remelted ingot is further processed by conventional metalworking techniques to produce bar, wire, sheet, plate and tubular
products.3
Basic Metallurgy
1. Composition
Four grades of unalloyed titanium known as Commercially Pure (CP)
Grade 1, 2, 3, or 4 are available with a stable alpha phase microstructure. The primary difference in composition is related to oxygen
content. The strength of unalloyed titanium increases as the oxygen
content increases from Grade 1 through Grade 4. Small quantities of
nitrogen and carbon tend to stabilize the alpha phase. The composition
requirements of the four unalloyed titanium grades are precisely controlled and documented in ASTM F 67 specification for surgical
implant material.4
Composition limits are also specified for Grade 1 ELI (Extra Low Interstitial), Grade 1, Grade 2, Grade 3, and Grades 4A (annealed) and 4B
(cold worked) in the ISO 5832-2 international standard.5 The ISO limits
are slightly different than ASTM F 67 limits and have been compared
as follows:
Unalloyed titanium composition limits for bar product according to ASTM F 67 and
ISO 5832-2 specifications
Grade 1
ELI
Grade 1
Grade 2
Grade 3
Grade 4,
4A, 4B
Nitrogen,
max
0.012
0.03
0.03
0.05
0.05
Carbon,
max
0.03
0.08
0.10*
0.08
0.10*
0.08
0.10*
0.08
0.10*
Hydrogen,
max
0.0125
0.0125*
0.015
0.0125*
0.015
0.0125*
0.015
0.0125*
0.015
Iron,
max
0.10
0.20
0.30
0.30
0.50
Oxygen,
max
0.10
0.18
0.25
0.35
0.40
Ti
Balance
Balance
Balance
Balance
Balance
Flat product such as sheet, strip, and plate are identical in composition
except a maximum hydrogen content of 0.015% is specified for all
grades in ISO 5832-2.
Maximum hydrogen content of 0.010% must be met for billet in
ASTM F 67 and ISO 5832-2. A billet is defined as a solid semi-finished
section with a cross sectional area greater than 10322 mm2 whose
width is less than 5 times its thickness.
Hydrogen content must be kept very low in titanium compositions.
Titanium cleaning operations which use nitric-hydrofluoric acid solutions are carefully controlled to eliminate hydrogen absorption during
pickling. A ratio of 10 parts nitric acid to 1 part hydrofluoric acid is
recommended.6
Unalloyed titanium usually contains a residual amount of iron in the
form of TiFe.7 This intermetallic compound increases the solubility limit
of hydrogen but does not have a dramatic effect on mechanical properties.8 The influence of iron content on the corrosion resistance can be
significant.9
ASTM F67 and ISO 5832-2 specifications permit a maximum iron
content from 0.10% to 0.50% depending on grade. Synthes titanium
bar product is specified to a lower maximum iron content, for enhanced corrosion resistance when compared to industry standards.
Detailed information on the effect of iron content on corrosion
resistance is included in the discussion on page 14.
2. Microstructure
Unalloyed titanium microstructures do not contain nonmetallic inclusions due to the highly sophisticated double or triple vacuum melting
practices that are used. Metallographic examination at 100X magnification typically reveals a complete absence of nonmetallic inclusions.
ASTM F 67 does not define unalloyed titanium microstructural features
but ISO 56832-2 requirements include a grain size of 5 or finer and the
absence of inclusions or foreign phases when examined at 100X
magnification.
A fine grain size is generally desired to provide a good combination
of tensile strength, ductility, and fatigue strength. Synthes unalloyed
titanium products are produced to a fine grain size requirement for
enhanced implant fabrication response and to provide an optimum
combination of mechanical properties.
The microstructure of unalloyed titanium can be altered by various
metallurgical treatments. An annealed microstructure is obtained
by heating the material to a defined temperature of around 700C
followed by a specific cooling cycle. The annealed micro-structure
4
Properties
1. Physical
Two important physical properties of unalloyed titanium for implant applications are the density and modulus of elasticity. A comparison2 with
wrought implant quality 316L stainless steel, wrought Co-28Cr-6Mo alloy, and wrought Ti-6Al-7Nb shows the properties set forth in the table
below.
The density of unalloyed titanium is 57% the density of wrought 316L
stainless steel and about 53% the density of wrought Co-28Cr-6Mo
alloy. The low density of titanium yields a weight reduction of nearly
50% when implants of similar dimensions are compared. The weight
reduction represents a patient comfort factor especially for large sized
implants.
Modulus of elasticity, or Youngs modulus, is a physical property of a
material that describes the stress per unit strain in the elastic region.
A material with a high modulus of elasticity will transfer less stress from
the implant to the bone. This produces a condition known
as stress shielding, which is undesirable because osteoporosis may
develop and promote refracture of the bone when the implant is
removed.10 However, recent work11 suggests that necrosis at the bone
plate contact surface may be responsible for some of the clinical
observations previously attributed to stress shielding.
The modulus of elasticity of unalloyed titanium is 5556% of 316L
stainless steel and 4243% of wrought Co-28Cr-6Mo alloy. Increased
stress transfer to bone is desirable but modulus of elasticity properties
are less important for fracture fixation implants with relatively small
cross-sectional areas.
Material
Density
(gm/cc)
Modulus of elasticity in
tension (MPa x 1000)
Ti Grade 1
4.51
103
Ti Grade 2
4.51
103
Ti Grade 3
4.51
103
Ti Grade 4
4.51
104
7.95
186
Wrought Co-28Cr-6Mo
8.29
241
Ti-6Al-7Nb
4.52
105
2. Tensile
The tensile properties of unalloyed titanium are dependent on grade
and type of metallurgical processing. ASTM F 67 specification outlines
the minimum mechanical properties that must be met in the annealed
or softest condition as a function of grade and product form. ISO
5832-2 international standard also covers annealed mechanical properties for Grades 1 ELI, 1, 2, 3, 4A, and includes Grade 4B in the cold
worked condition.
The minimum tensile properties of unalloyed titanium Grades 1 ELI, 1,
2, 3, 4, 4A, and 4B, implant quality 316L stainless steel (ASTM F 138),
wrought Co-28Cr-6Mo alloy (ASTM F 1537), and Ti-6Al-7Nb alloy
(ASTM F 1295) bar product in the annealed condition have been
compared as follows:
Material
Ultimate
tensile
strength
(MPa)
0.2%
yield
strength
(MPa)
Elongation
x 4D or 4W*
(%)
Reduction
of area**
(%)
Ti Grade 1 ELI
200
140
30
Ti Grade 1
240
170
24
30
Ti Grade 2
345
275
20
30
Ti Grade 3
450
380
18
30
Ti Grade 4
550
483
15
25
Ti Grade 4A
550
483
15
Ti Grade 4B
680
520
10
480
170
40
Wrought Co-28Cr-6Mo
897
517
20
20
Ti-6Al-7Nb
900
800
10
25
* Alternatively, a gauge length of 5.65 So, where So is the original cross-sectional area, may be used
** Not specified in ISO 5832-2 or ASTM F 138
Cold worked condition
Properties continued
Minimum Tensile
Strength (MPa)
900
800
700
600
Synthes
500
400
Industry
8
10
12
14
16
18
20
Additional mechanical property requirements for unalloyed titanium sheet, strip, and
plate in the annealed condition
Bend test mandrel diameter (mm)
ASTM F 67
grade
Maximum 0.2%
yield strength (MPa)
Under 1.8 mm
thick
1.8 mm to 4.75 mm
thick
310
3T*
4T
450
4T
5T
550
4T
5T
655
5T
6T
Properties continued
Minimum yield strength and elongation requirements for annealed titanium wire
< 3.18 mm diameter
Diameter (mm)
Grade
Yield strength
(0.2% offset),
MPa
1
2
3
4
170
275
380
483
15
12
10
8
1
2
3
4
---------
12
10
8
8
1
2
3
4
---------
10
8
6
4
Elongation %
Size variations and out-of-round tolerances are also compiled for wire diameters < 3.18 mm in ASTM F 67.
10
3. Fatigue
Fatigue is defined as the process of progressive, permanent structural
change occurring in a material that is subjected to alternating stresses
and strains.13 The alternating stress and strain effects are usually localized and may produce cracks or complete fracture after a sufficient
number of cycles. Unalloyed titanium fatigue life, or number of loading
cycles sustained before failure, is influenced by many factors including
composition,14 grain size,15 processing history,16 surface\finish,17 residual
surface stress,18 and ultimate tensile strength.19 Major test dependent
variables include type of alternating load (rotating-beam; plane bending; tension-compression), specimen geometry, frequency, and test
environment.
Fatigue testing of orthopaedic implants is generally performed at a
low frequency of 35 cycles/sec and may include a 0.9% saline or
biological test environment. This is somewhat different than the test
procedures typically used for fatigue characterization of bar and sheet
product. Because of the complexity of fatigue testing, only a brief
overview will be presented.
The following data documents the plane bending fatigue data of unnotched, 1.0 mm thick unalloyed titanium sheet as a function of tensile
strength:
Plane bending fatigue data for unnotched 1.0 mm thick unalloyed titanium sheet19
Ultimate tensile
strength (MPa)
Condition
Annealed
Cold rolled
Plane bending
fatigue strength (MPa)
371
246
402
235
432
284
468
284
510
265
667
314
667
343
745
334
766
343
772
383
820
383
Frequency: 58 cycles/sec
Properties continued
The fatigue strength is the maximum stress that can be sustained for a
specific number of cycles without failure, the stress being completely
reversed within each cycle unless otherwise stated. The plane bending
fatigue strength of the 1.0 mm unalloyed titanium sheet increases as
the ultimate tensile strength increases. The fatigue strength varies between 4566% of the UTS, and this index is known as the endurance
ratio.
Many metallurgical factors and specific test variables exert a strong influence on the fatigue strength that is obtained for implant materials.
The fatigue properties of unalloyed titanium, implant quality 316L
stainless steel, and a wrought cobalt base implant alloy have been
documented .20 In this study, Grade 3 titanium had a higher fatigue life
than 316L stainless steel in the low load range. The fatigue results
were highly dependent on loading conditions.
The endurance limit is the maximum stress below which a material can
presumably endure an infinite number of stress cycles. Comparative
fully reversed flexural fatigue results for various implant materials have
been compiled 21 as follows:
Condition
10 7 cycles (MPa)
CP Ti
Annealed
241 379
Cold worked
310 448
Co-Cr-Mo
Cast
241 310
Ti-6Al-4V
Annealed
379 448
12
4. Corrosion
The superior corrosion resistance of unalloyed titanium and titanium
alloys compared to iron or nickel based implant alloys is well documented in the literature. 22 The referenced study measured the anodic
polarization behavior of a number of implant materials versus a Saturated Calomel Electrode (SCE) in a physiological solution. Tabulated
corrosion results as follows:
Breakdown potential for implant metals in Hanks solution at 37C
Breakdown
Potential
(Volts)
2.4
2.0
1.6
1.2
0.8
0.4
0
316L
Co-Cr-Mo
Ti-6Al-4V
Ti
Properties continued
Corrosion
rate
(gm/m2/hr)
0.20
0.15
0.10
0.05
0.00
0.02
0.06
0.10
0.14
For many materials, localized corrosion may occur within crevices and
small cavities on metal surfaces exposed to aggressive solutions containing dissolved oxygen and chloride ions. The data below compares 316L
stainless steel with unalloyed titanium Grade 2 under accelerated
exposure conditions .24
Crevice corrosion resistance in geothermal brine with 100 ppm
oxygen at 232C for 15 days
Material
316L Stainless Steel
Ti Grade 2
0.18
Plate
Screws
Total
Ti
0.018 0.004
0.016 0.009
0.040 0.016
0.138 0.050
0.122 0.038
0.260 0.075
The weight loss results in the referenced study have been converted to
fretting volume to account for the density differences. Each screw and
each two-hole plate was individually weighed, in addition to each three
component combination. Hence, there is a slight difference between
plate + screw cumulative volume loss and total plate/screw volume
loss. The fretting resistance of the titanium plates and screws was
superior to 316L stainless steel plates and screws in this study under
accelerated laboratory fretting conditions.
An accelerated form of corrosion known as galvanic corrosion can
occur in a mixed metal system due to the difference in the electrochemical potential between the two materials. Emergency clinical situations may be encountered that may require the use of 316L stainless
steel and unalloyed titanium for multicomponent device applications.
Consequently, a clinical study was conducted with Synthes implant
quality 316L stainless steel screws and Synthes unalloyed titanium bone
plates. 27 No clinical disadvantage was observed in the study for this
specific combination of implants.
The extent of galvanic corrosion that may be experienced with a mixed
metal system is difficult to predict on the basis of values extracted from
the electromotive series. This is highlighted in a report by Kruger 28 that
states Even if one uses a more relevant series of potentials, there is
no assurance that one can reliably predict the extent of corrosion
caused by a bimetallic couple. Solar concluded that implant quality
316L exhibited multiple pitting in all tests when coupled with itself, a
titanium alloy, or cast Co-Cr-Mo .23 According to Solar, similar results
were obtained by Levine and Staehle who concluded problems can
occur with any of the widely used metals, however, especially if metals
are mixed. Galvanic corrosion effects are also dependent on the relative ratio of the anodic to cathodic areas.
15
Properties continued
5. Biocompatibility
As early as 1940, Bothe and colleagues concluded that unalloyed titanium pegs were well tolerated in an animal model and the biocompatibility was similar to stainless steel or Co-Cr-Mo alloy. 29 Leventhal worked
with rabbits and rats and reported in 1951 that titanium was inert and
appeared to be ideal for fraction fixation. 30 Brunski concluded that good
tissue response was obtained when pure titanium dental implants were
evaluated in beagle dogs. 31 Organ culture studies at the Laboratory
for Experimental Surgery. 32 have demonstrated the excellent growth
development of embryonic rat femora implanted with titanium rods.
A study by Williams and Meachim 33 involved a large series of retrieved
human implants during the period of 1967 to 1972. No corrosion was
noted in any of the 49 titanium implants but 54% (64 out of 119) of the
stainless steel implants exhibited varying degrees of corrosion.
About 90% of the endosteal implants inserted worldwide are titanium
and Weiss has reported that unalloyed titanium dental implants are
being used routinely with clinical success. 34
Metal sensitivity reactions must also be considered. Dobbs and Scales
have reported that to their knowledge there are no reports which suggest that metal sensitivity or adverse reactions of any kind are associated
with titanium implants.35 This is in contrast to various clinical studies
which have shown that metal sensitivity reactions have been observed
with 316L stainless steel and Co-Cr-Mo implants. Preoperative patch
testing of 212 patients undergoing total hip replacement indicated that
6.6% were sensitive to nickel, cobalt, and chromium .36 There was some
indication that metal sensitivity was provoked in four patients after implantation. A more sophisticated metal sensitivity test known as leukocyte migration has shown 18% sensitive to nickel, 15% sensitive to
cobalt, and 3.5% sensitive to chromium in a study with 629 patients. 37
Synthes unalloyed titanium implants are recommended in situations
where metal sensitivity is preoperatively verified or where 316L stainless
steel implants have provoked an allergic patient response.
Unalloyed titanium also exhibits unique biocompatibility properties
which include soft tissue and bone adhesion to the titanium surface.38, 39
16
6. Surface
Titanium that is exposed to air or water spontaneously forms a titanium
oxide film which is about 0.5 to 0.6 nanometers thick .43 A nanometer
is an extremely small unit of length equal to 1 x 10-9 meter. The exceptional stability and corrosion resistance of this passive layer has been
previously discussed.
Synthes unalloyed titanium implants are chemically treated in an electrolytic process known as anodizing to increase the thickness of the
naturally occurring titanium oxide film. The anodized film consists of
titanium oxide and is about 4060 nanometers thick. Various colors can
be produced in the anodizing process and this is a function of the oxide
thickness. Light interference within the oxide film is responsible for the
color that is obtained. Standard Synthes titanium implants are anodized
in a manner that creates a consistent and reproducible gold appearance,
although other colors can be produced.
Iron contamination may be present on the titanium surface as a result
of the implant machining or fabricating operations. Corrosion pitting
failures have been attributed to this type of surface contamination. 2
The chemical conditioning treatments that are a part of the anodizing
process remove surface contaminants that may be present from the
various manufacturing operations.
Rahn and coworkers 44 have investigated the relative amount of tissue
growth on Synthes titanium discs. The results indicated that mechanically polished, chemically polished, and anodized surfaces promoted similar animal cell growth patterns. It is expected that similar cellular
adhesion properties would be obtained for these relatively smooth
titanium surfaces.
The color readily distinguishes Synthes titanium implants from Synthes
316L stainless steel implants and this is considered an additional benefit
derived from the anodizing treatment. The gold appearance is aesthetically appealing, and the implants display reduced external visibility when
epidermal coverage is minimal.
17
Clinical Features
Synthes unalloyed titanium implants offer major clinical advantages which have been
summarized as follows:
Features and clinical advantages of Synthes unalloyed titanium implants
Material feature
Clinical advantage
Permanent implants
Unique biocompatibility
Nonallergenic
Low density
Lightweight implants
Good ductility
Easily contoured
Four grades
Sterilization
Implants may be sterilized by any of the standard methods such as
steam autoclave, ETO, gamma radiation, electron beam, and RF
discharge.
Implant handling
Excessive fingerprint contamination from handling may produce slight
discoloration after repeated steam autoclave cycles. No adverse effects
are related to this change in surface appearance.
Diagnostic imaging
X-radiography, Magnetic Resonance Imaging, CT Scans, and PET scans
can be utilized. MRI scan resolution is superior to 316L stainless steel
because titanium produces less starburst, or signal interference.
Implant retrieval
Occasional black deposits (wear debris) may be observed at implant removal sites. No adverse tissue reaction is associated with this clinical
observation. 35
18
References
19
References continued
20
21
References continued
22
Glossary
23
Glossary continued
24
VACUUM ARC REMELTING. A melting process in which an electric arc is used to remelt an electrode inside a vacuum chamber.
YIELD STRENGTH. In tensile testing, the stress at which the
stress-to-strain ratio exhibits a specified deviation, usually designated
as 0.2% offset.
25
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