Implant Materials.

Wrought 18% Chromium

14% Nickel2.5% Molybdenum
Stainless Steel.

Third Edition
John Disegi
Third Edition
Jan 2009

About the Cover

A portion of the Periodic Table depicts various
major implant alloy elements.
Face-centered-cubic (FCC) crystal structure
of stainless steel.
Table of Contents

Introduction 2

Basic Metallurgy 1. Composition 4

2. Microcleanliness 5

3. Microstructure 6

Properties 1. Physical 9

2. Tensile 10

3. Fatigue 12

4. Corrosion 14

5. Biocompatibility 18

6. Surface 19

Clinical Features 21

References 22

Glossary 26
Introduction

During World War II there was considerable interest in identifying

satisfactory stainless steel implant materials to repair bone fractures
associated with wartime injuries. Murray and Fink recommended Type
302 stainless steel 1 to the U.S. Army and Navy in 1943. After the war,
Peterson (1947) reviewed the clinical performance 2 of plates and
screws used for fracture treatment by the Army. He concluded that
18-8 SMo which contained 18% chromium + 8% nickel + 2%
molybdenum provided the best combination of properties. In the early
50s, Blunt et al. evaluated various metals that were implanted in dogs 3
and Type 316 appeared to be the best choice. This landmark effort set
the stage for the widespread use of Type 316/316L stainless steel for
surgical implant applications. ASTM F 55-65T 4 was eventually pub-
lished in 1965 to define the metallurgical requirements for Type 316
(Grade 1) and Type 316L (Grade 2) while ASTM F 56 for sheet and
strip 5 was published one year later.
The air-melted implant compositions performed reasonably well but it
was recognized that premium melted material would be an advantage.
Remelted material was capable of providing improved homogeneity,
controlled microcleanliness, and better corrosion resistance. ASTM F
138 for special quality bar and wire was published in 1971 6 while
ASTM F 139 for special quality sheet and strip 7 was issued in 1976.
An AO Bulletin entitled Characteristics of the Stainless Steel AO
Implants was published in 1975 by O. Pohler and F. Straumann 8.
This bulletin documented the composition and metallurgical features
of AO implant quality stainless steel that was used for surgical implants
during this timeframe.
Stainless steel melting practice typically includes electric arc melting to
produce an electrode followed by argon oxygen decarburization (AOD)
and premium remelting of the electrode into individual ingots. The in-
gots are hot pressed or rotary forged into intermediate-sized billets and
blooms for further processing such as hot rolling. Hot rolled round,
flat, and profiles may be further processed into bar, wire, sheet, strip,
and special shapes using conventional wrought stainless steel metal-
working methods. Specialty stainless steel cold finishing operations
such as annealing, cleaning, and cold drawing are used for bar and
wire while bar finishing may also include straightening, centerless
grinding, and polishing. Wide flat rolled strip product may be straight-
ened, slit, edged, and cut to length.

2
Other wrought stainless steels such as nitrogen strengthened high
manganese alloys 9 -10 may also be used for the manufacture of surgical
implants but the present discussion will focus on AO 18% chromium-
14% nickel-2.5% molybdenum stainless steel, which is also known as
implant quality 316L stainless steel in the United States and implant
quality DIN 1.4441 stainless steel in Europe.

3
Basic Metallurgy

1. Composition
The chemical requirements for implant quality stainless steel are
documented in ASTM F 138 11 and ISO 5832-1 12 specifications. A simi-
lar analysis of stainless steel is also available as ASTM A276 13 commer-
cial quality alloy with different composition limits and microstructure
features when compared to implant quality. The composition limits for
implant quality and commercial quality stainless steel are compared.

Comparison Between Implant Quality and Commercial Quality Stainless Steel

Chemical Requirements (%)A

Implant Quality Commercial Quality

Element ASTM F 138 ISO 5832-1 ASTM A 276

C 0.030 0.030 0.030

Mn 2.00 2.0 2.00

P 0.025 0.025 0.045

S 0.010 0.010 0.030

Si 0.75 1.0 1.00

Cr 17.00-19.00B 17.0-19.0B 16.00-18.00

Ni 13.00-15.00 13.0-15.0 10.00-14.00

Mo 2.25-3.00B 2.25-3.5B 2.00-3.00

N 0.10 0.10 0.10

Cu 0.50 0.50

Fe Balance Balance (Balance)

A. Maximum, unless otherwise noted B. %Cr + 3.3 X %Mo 26

The ASTM and ISO implant composition limits are nearly identical with
slight differences in maximum silicon and molybdenum content. The
following discussion highlights the relative importance of implant
quality ASTM F 138 composition limits when compared to commercial
quality ASTM A 276.
Lower phosphorus content provides somewhat better ductility, espe-
cially for the majority of surgical implants that are moderately or highly

4
cold worked. The reduction in maximum sulfur content from 0.030%
to 0.010% has a favorable effect on the volume fraction of sulfide
inclusions. The importance of manganese sulfide (MnS) control in
implant quality stainless will be reviewed later in the discussion
regarding surface properties. Reduced silicon content is responsible for
a decrease in silicate-type inclusions and provides better austenite
stability. Higher chromium content has a favorable effect on corrosion
resistance but has a negative influence on austenite stability. The
nominal nickel content in implant quality stainless is significantly higher
than in commercial quality and is primarily responsible for maintaining
a completely austenitic microstructure. High nickel content minimizes
the tendency to form delta ferrite (-ferrite) while cold working
response is decreased because of the inverse relationship with nickel
content. The minimum 2.25% molybdenum content and higher
chromium content ensures that the compositional requirement
%Cr + 3.3 X %Mo 26 will be met. This is a unique requirement for
implant quality stainless steel and will be described in more detail in
the corrosion discussion. The limitation on copper content is a second-
ary method of controlling tramp elements that may be present in revert
material that is used in the melting process.
2. Microcleanliness
ASTM and ISO standards establish nonmetallic inclusion limits for im-
plant quality bar, wire, sheet, and strip when evaluated according to
Method A of ASTM E 45 14. Microcleanliness limits are tabulated.

Inclusion Limits for Implant Quality Stainless Steel

Maximum Limits

Inclusion Type Thin Heavy

A (Sulfide) 1.5 1.0

B (Alumina) 1.5 1.0

C (Silicate) 1.5 1.0

D (Globular Oxide) 1.5 1.0

Bar and wire inclusion ratings are usually performed on billet or bar
samples while sheet and strip are rated at an intermediate hot rolled
stage. In the past, double vacuum melting such as vacuum induction
melt (VIM) + vacuum arc remelt (VAR) have been used to ensure that

5
Basic Metallurgy continued

the inclusion limits would be met. The implant quality suppliers devel-
oped a significant database over the years that verified double vacuum
melting was not required to meet the inclusion limits. Alternate
melting practices were established for implant quality stainless which
included electric arc + argon oxygen decarburization (AOD) refining +
VAR in the United States. European melt practice was similar but
included electric arc + AOD or vacuum ladle refining + electroslag
remelt (ESR). VAR practice tends to minimize Type D globular oxides
because oxygen content is reduced during vacuum remelting. The
volume fraction of Type A sulfides are usually lower in ESR ingots
because the slag layer can be formulated to desulfurize the arc melted
electrode.

3. Microstructure
Carbides
Carbides of the M6C type have been observed 15 in the higher
carbon Type 316 alloy after prolonged heating in the 800 1200F
sensitization range. M6C tends to precipitate intergranularly and has
an adverse effect on intergranular corrosion resistance. This observa-
tion provided technical justification for the eventual widespread use of
low carbon 316L rather than higher carbon 316 for surgical implants.
Each lot of implant quality stainless steel must be capable of passing
Practice E of ASTM A 262 16 intergranular corrosion susceptibility test.
Delta Ferrite/Chi/Sigma
ASTM F 138, ASTM F 139 and ISO 5832-1 implant standards specify
that implant microstructures must contain no -ferrite, chi, or sigma
phases when examined at 100X magnification. Longitudinal specimens
may be etched in a mixture of copper chloride, hydrochloric acid, and
ethanol to reveal the presence of -ferrite. An electrolytic etch in potas-
sium hydroxide may also be used to confirm -ferrite which will be
visible as a blue stain. Delta ferrite is considered an objectionable
secondary phase in implant quality stainless steel because of inferior
corrosion resistance and magnetic permeability when compared to
the austenitic matrix. Chi and sigma phases may be identified according
to methods outlined in ASTM E407 Practice for Microetching Metal
and Alloys.
The specialty steel producers may also use weld metal constitution
diagrams such as Delong or Schaeffler to estimate the amount of
-ferrite in each remelted ingot. Numerous calculations over the years
have indicated that -ferrite will typically not be observed in the micro-

6
structrue of homogeneous remelted material when the calculated delta
ferrite content is less than 1.5% based on chromium and nickel equiv-
alents. The calculated -ferrite values represent a preliminary estimate
since finish mill products must be metallographically examined to verify
that -ferrite is not present in the microstructure.
Grain Size
Implant quality bar, wire, sheet, and strip must meet a grain size of five
or finer according to prevailing ASTM standards. The actual grain size
area becomes smaller as the ASTM grain size number increases. A fine
grain size is desirable to provide a good combination of tensile and
fatigue properties. The specialty stainless suppliers measure and certify
the ASTM grain size after the last annealing operation. However, the
majority of implant quality stainless steel is ordered in the moderate or
highly cold worked condition. The implant standards specify that the
grain size should be measured on a transverse sample if the material is
rated in the cold worked condition. This compensates somewhat for
the grain elongation that occurs in the longitudinal plane during unidi-
rectional cold working. Implant device manufacturers may also specify
restrictions on grain size uniformity. For example, a grain size of ASTM
7.5 or finer may be acceptable as long as the material does not exhibit
duplex grains that differ by more than 2.5 ASTM grain size ratings.
Photomicrographs of annealed implant quality stainless steel with an
ASTM grain size of 6.5 and moderately cold worked implant quality
stainless steel with a grain size of ASTM 6.5 are shown. The photo-
micrographs were provided by Dr. Lyle Zardiackas, University of
Mississippi Medical Center.

Etched Transverse Microstructure of Annealed Etched Transverse Microstructure of Cold

Implant Quality Stainless Steel (100X) Worked Implant Quality Stainless Steel (100X)

7
Basic Metallurgy continued

Medical device manufacturers commonly recertify lots of implant

quality stainless steel as part of their Quality Assurance program. Some
small diameter wire products may be ordered in the extra hard condi-
tion with an ultimate tensile strength around 1400 MPa. It is extremely
difficult to accurately measure austenite grain size in material with this
amount of microstructure distortion. In these instances, the recertifica-
tion laboratory will normally document the grain size rating certified by
the supplier.
Magnetic Permeability
The microstructure and composition will also influence the magnetic
permeability of stainless steel. Some types of austenitic stainless steel
will become magnetic during cold working or fabrication. The metal
deformation that occurs during cold working can create a solid state
austenite to martensite phase transformation. Martensite is a ferro-
magnetic or highly magnetic phase. An increase in magnetic perme-
ability due to cold working or the presence of a secondary magnetic
phase such as -ferrite are not desirable since patients with implanted
devices may be subjected to magnetic resonance imaging (MRI)
procedures. Microstructures must be completely nonmagnetic to
avoid implant heating or movement of the implant during MRI.
Stainless grades which contain molybdenum will not become magnetic
during cold working because the stabilized austenitic microstructure
is resistant to strain induced martensite phase transformation at room
temperature. Also, implant quality stainless steel does not contain sec-
ondary magnetic phases in the microstructure. Magnetic permeability
measurements 17 have confirmed that negligible magnetic response is
obtained with highly cold worked (extra hard) AO implants.

8
Properties

1. Physical
Important physical properties18 are compiled for implant quality
stainless steel.

Physical Properties of Implant Quality Stainless Steel

Mean Coefficient
Modulus of of Thermal Thermal
Elasticity Electrical Expansion Conductivity
Density in Tension Resistivity From 293 873K at 373K
(g/cm3) (GPa) (microhmmm) (10-6/K) (Wm/m2K)

7.95 186.4 740 18.5 16

The density of stainless steel is not critical since the weight of relatively
small-sized fracture fixation implants is not considered a major material
factor. The modulus of elasticity is a measure of the stress per unit
strain in the elastic region. The relative stiffness of an implant material
is directly related to the modulus of elasticity. The stiffness increases as
the modulus increases. The modulus of stainless steel is about 80%
greater than unalloyed (Commercially Pure) titanium. Stainless implants
will be significantly stiffer than titanium implants of the same general
dimensions. In addition, the implant design will also influence the
stiffness or flexibility of an implant system.

9
Properties continued

2. Tensile
The tensile properties of implant quality stainless steel bar and wire
are specified in the latest revisions of ASTM F 138 and ISO 5832-1.
Although the size ranges may differ, the tensile property limits speci-
fied in ASTM and ISO material standards are essentially the same.

Tensile Properties of Implant Quality ASTM F 138 Bar and Wire and ISO 5832-1 Bar

Diameter Ultimate Minimum Minimum

or Tensile 0.2% Yield Elongation in
Thickness Strength Strength 4D or 4WA
Standard Condition (mm) (MPa) (MPa) (%)

ASTM F 138 Annealed 1.60 min 490 190 40

ISO 5832-1 Annealed All 490 690 190 40

ASTM F 138 Cold Worked 1.60 38.1 min 860 690 12

ISO 5832-1 Cold Worked 22 8601100 690 12

ASTM F 138 Extra Hard 1.60 6.35 min 1350

ISO 5832-1 Extra Hard 8 min 1400

A. 4D = 4 X diameter; 4W = 4 X width. Alternately, a gage length corresponding to ISO 6892 19 may be used.

The ISO bar standard includes a maximum limit for ultimate tensile
strength in the annealed or coldworked conditions, which is not a re-
quirement in the ASTM specification. The size differences are primarily
related to product definitions since ASTM defines a size less than 1.60
mm diameter as fine wire while ISO defines all sizes less than 2 mm di-
ameter as wire. Additional tensile requirements for ASTM fine wire and
various ISO wire sizes are specified in the respective material standards.
The annealed condition represents the lowest strength condition.
This condition is generally preferred for the manufacture of cerclage
wire and reconstruction plates where a low strength is satisfactory
but a maximum amount of ductility is needed. Annealed tensile
properties for cerclage wire are specified in a separate ASTM F 1350
specification20.
The cold worked condition is an intermediate strength condition used
for the manufacture of bone screws, bone plates, intramedullary nails,
etc. The extra hard condition is the highest strength condition used
primarily for small diameter wire products such as Kirschner wire and

10
Schanz screws where increased resistance to permanent bending
deformation (high yield strength) is most important.
Mechanical properties for sheet and strip are covered in ASTM F 139 21
and ISO 5832-1 industry standards. Sheet and strip minimum tensile
properties are tabulated as follows.

Tensile Properties of Implant Quality Stainless Steel Sheet and Strip

Ultimate Minimum Minimum

Tensile 0.2% Yield Elongation
Strength Strength in 50 mmA
Standard Condition (MPa) (MPa) (%)

ASTM F 139 Annealed min 490 190 40

ISO 5832-1 Annealed 490 690 190 40

ASTM F 139 Cold Worked min 860 690 10

ISO 5832-1 Cold Worked 8601100 690 10

A. Or 5.65 So, where So is the original cross sectional area, in mm2.

A comparison of ASTM F 139 with ISO 5832-1 indicates identical

minimum tensile properties for sheet and strip in the annealed or cold
worked condition. The ISO requirements for sheet and strip also in-
clude a maximum ultimate tensile strength for the annealed or cold
worked conditions.
Implant quality stainless steel may be cold worked to increase the
ultimate tensile strength. Data has been published by Carpenter Tech-
nology 18 that defines the mechanical property relationships for wire
product with different levels of cold work. The ultimate tensile strength,
0.2% yield strength, and hardness increase as the percentage of cold
work increases. The % elongation tends to decrease as the % cold
work increases. The % reduction of area is actually a better measure of
the ductility than % elongation and the decrease in the reduction of
area is more consistent as a function of increasing cold work. These
types of mechanical property relationships are very typical for austenitic
stainless steels.

11
Properties continued

Typical Tensile Properties and Hardness of Implant Quality Stainless Steel as a

Function of Cold Work

Ultimate 0.2%
Tensile Yield Reduction
Cold Work Strength Strength Elongation of Area Hardness
Condition (%) (MPa) (MPa) (%) (%) (HRC)
Annealed 0 586 248 57 88 88 HRB
Cold 35 862 793 18 72 26
Worked 48 1000 827 16 69 32
52 1034 848 16 65 34
60 1103 883 16 62 36
70 1172 896 17 60 38
80 1241 945 13 57 40

3. Fatigue
Fatigue is the phenomenon leading to fracture under repeated or fluc-
tuating stresses having a maximum value less than the ultimate tensile
strength of the material. The fatigue loads are well below the level
which normally would be required to cause fracture within a single
load cycle. The fatigue cycle is the time interval during which the stress
is regularly repeated. There are many material variables that influence
fatigue test results such as grain size, processing history, surface finish,
and degree of cold work. Testing variables include type of alternating
load, specimen geometry, frequency, and test environment.
A common method of expressing the fatigue properties of a material is
known as the S-N curve. The S-N curve is a best-fit plot of the individ-
ual test values where S refers to the applied cyclic stress and N is the
number of cycles required to fracture the test specimens. S-N curves
for AO implant quality stainless steel are reproduced from previous
research work performed by O. Pohler 22 at Stratec Medical. The fatigue
curves describe the stress concentration (MPa) versus the number of
cycles to failure (N) for fully reversed bending fatigue of recrystallized
(annealed) or cold worked implant quality stainless steel specimens in
air and in Ringers solution. Ringers solution is a physiological solution
containing a mixture of sodium, potassium, and calcium chlorides plus
bicarbonates that approximates the electrolyte and corrosive environ-
ment in the human body at a pH of 6.5. The fatigue test results

12
confirm that the cold worked condition provides a higher fatigue life
when compared to the annealed or softest condition. This trend is gen-
erally observed for most non-brittle engineering materials that can be
cold worked to develop higher ultimate tensile strengths. The use of a
more severe testing environment such as Ringers solution, which con-
tains chloride ions, shows a general decrease in the cycles to failure for
a given stress concentration when the material is in the cold worked
condition. The aggressive Ringers test environment does not have a
significant effect on fatigue results for specimens in the annealed
condition.

1000 125
Cold worked in air
Cold worked in Ringers
900 Recrystallized in air
100
Stress concentration, MPa

Recrystallized in Ringers
Stress concentration, ksi

700 75

500 50

25
300

0
100
103 104 105 106 107
Number of cycles to failure

13
Properties continued

The endurance limit is the maximum stress below which a material can
presumably endure an infinite number of stress cycles. Fully reversed
(R=-1) endurance limit values have been published 23 for implant quality
stainless steel as follows:

Endurance Limit for Implant Quality Stainless Steel

Flexural Endurance Limit

Condition Cold Work (%) at 107 Cycles (MPa)
Annealed 0 179
Cold Worked 30 379
60 448
80 483

The flexural fatigue test results verify that the endurance limit increases
as the percentage of cold work increases. There is a limitation regard-
ing the amount of cold work that can be introduced into implant
quality stainless steel material. Cross-sectional area is a factor since
only small- to moderate-size cross sections can be obtained in the
highly cold worked condition. Large cross-sectional areas cannot be
cold worked the same amount due to processing and equipment
limitations. Many fracture fixation implants require a certain balance
between strength and ductility (i.e. ability to contour a bone plate) so
that it is not always desirable to specify the highest attainable tensile
strength.

4. Corrosion
Pitting
The Composition section referred to a term known as the composi-
tional index %Cr + 3.3 X %Mo 26 which is a unique feature of
implant quality stainless steel material. The index was derived from
a study published by Steinemann in 1980 24 which determined that
adequate pitting resistance in the body could only be assured if this
relationship was satisfied. The increased chromium and molybdenum
content of implant quality stainless steel provide improved corrosion
properties in a chloride-containing physiological environment. Calcula-
tions indicate that implant quality stainless steel with a nominal
17.50% chromium content must contain at least 2.60% molybdenum
to meet the compositional formula.

14
Stress Corrosion Cracking
Stress corrosion cracking (SCC) is a form of corrosion failure that can
occur under the combined action of corrosion and stress. The stress
may be the result of residual stress in the material and/or the applied
stress related to the end-use application. One common test method to
evaluate SCC involves the use of smooth hour-glass-shaped specimens
that are subjected to slow strain rate tensile tests in very aggressive
chemical solutions at elevated temperatures. Typical SCC tests may be
performed in boiling solutions of 45% magnesium chloride at 154C.
The presence of high chloride concentrations and elevated tempera-
tures accelerate the occurrence of SCC.
Implant quality stainless steel has been evaluated for SCC by Sheehan
et al. 25 under laboratory conditions that are more representative of the
chloride concentration and temperature that are relevant for surgical
implants. Electropolished hour-glass specimens of cold worked implant
quality were pulled to failure in lactated Ringers solution at 37C and
strain rates of 10 5, 10 6, and 10 7 cm/cm/sec. The slow strain rate
tension test results reported by Sheehan were as follows:

Slow Strain Rate Test Results for Implant Quality Stainless Steel

Ultimate Reduction
Strain Rate Tensile Strength Elongation of Area
(cm/cm/sec) (MPa) (%) (%)
10 5 956 27 43
10 6 947 31 49
10 7 930 24 47
10 6 934 28 43a
10 6 947 27 46b
a. HCl acidified to pH of 2 b. FeCl3 acidified to pH of 2

A material is considered to be susceptible to SCC if a decrease in

strength and/or ductility is observed with a decreasing strain rate or at
lower pH values. The results indicate there is no significant change in
strength or ductility as a function of strain rate or pH level. SCC did not
occur with cold worked implant quality stainless under these test con-
ditions which were meant to simulate a neutral and acidified in vivo
corrosion environment. Examination of fractured specimens confirmed
that the fractures were ductile cup-cone fractures with no evidence of
secondary branching associated with SCC.

15
Properties continued

Fretting
The excellent corrosion resistance of stainless steel is related to the
presence of a chromium oxide layer at the surface of the alloy. This cor-
rosion resistant layer is referred to as the passive film. Fretting corrosion
is a form of corrosion that can occur when the passive film is mechani-
cally disrupted or removed. The removal of the passive film due to
mechanical action in a corrosion environment tends to accelerate the
overall corrosion rate and this effect is known as fretting corrosion.
Fretting corrosion can occasionally be observed when bone plates and
screws are clinically retrieved. Typically, the contact of the underside of
the screw head with the bearing surface surrounding the plate hole
creates a fretting corrosion condition due to localized passive film
disruption.
S. Brown and K. Merritt 26 have reported laboratory fretting weight loss
results and standard deviations for stainless steel DCP plates and
screws. The tests were performed with two-hole plate specimens that
were cut from DCP implants and cortical bone screws at one cycle per
second for a total of 806,000 cycles. Each two-hole plate and each
screw was weighed, in addition to each three-component combination.
Hence, there is a difference between the plate + screw versus total
weight loss values.

Stainless Steel DCP Fretting Weight Loss After 14 Days

Number of
Samples Plate Screw Total
Solution (N) (mg) (mg) (mg)
0.9 % saline 5 1.23 0.37 1.21 0.30 2.22 0.60
+ 10 % serum 4 0.14 0.07 0.22 0.08 0.32 0.11

Results indicate a significant reduction in weight loss when 10% calf

serum was added to the 0.9% saline solution. The weight loss reduc-
tion may be a result of a lower coefficient of friction at the fretting
interface because of the lubricating quality of the serum. The refer-
enced study also reported that fretting torque loads of 260 N and
560 N were statistically equivalent but fretting torque loads of 860 N
provided significantly lower weight loss. The torque load anomaly was
explained on the basis of minimal fretting at low loads while the equip-
ment design tended to minimize relative motion at the highest torque

16
load. The laboratory fretting study highlights the observation that
fretting corrosion is a complicated phenomena which is influenced by
many variables. Proper design of implant dimensional features and op-
timum surface finishing techniques can minimize the occurrence of
clinical fretting corrosion of stainless steel plates and screws.
Galvanic
The well known AO study published in 1975 by Dr. Thomas Ruedi 27
examined the clinical implications of mixing stainless steel and titanium
implants. The retrospective study was based on a group of 519 human
fractures of the upper and lower limbs that utilized titanium DCP
plates + stainless screws. A follow-on study involved a series of 75 tibia
platings that evaluated various metal and mixed metal combinations.
The relative advantages and disadvantages were summarized on the
basis of clinical, radiological, and implant tissue retrieval studies. Less
titanium wear debris was observed in surrounding tissues for stainless
screws + pure titanium plates when compared to pure titanium plates
and screws. This suggested that fretting corrosion resistance was im-
proved for this specific mixed implant combination. However, stainless
steel corrosion and tissue discoloration were experienced with the
mixed metal system. It was concluded that the unalloyed titanium
monosystem demonstrated significantly better tissue biocompatibility
when compared to the stainless screw + unalloyed titanium plate
system.
Galvanic corrosion may occur as a consequence of the existing poten-
tial difference between dissimilar biomaterials. The following informa-
tion has been extracted from a 1991 publication by M. Barbosa 28.
Two methods commonly used to estimate the effect of mixing metals
include the use of mixed potential theory and current flow measure-
ments. The application of mixed potential theory relies on the interpre-
tation of polarization diagrams and is beyond the scope of this review.
Current flow measurements or in vitro accelerated corrosion tests can
be used to rank materials in terms of corrosion resistance and to decide
whether is is safe or unsafe to use various dissimilar couples. From
several published papers it is possible to conclude that most materials
coupled with implant quality stainless steel are unsafe. The data has
been summarized by M. Barbosa as follows:

17
Properties continued

Predicted Behavior of Galvanic Couples

Biomaterial Couple Behavior

Ti-6Al-4V + Carbon Safe
Ti-6Al-4V + Vitallium Safe
Stainless Steel + Carbon Unsafe
Stainless Steel + Ti-6Al-4V Unsafe
Stainless Steel + Vitallium Unsafe

Vitallium is a cobalt based alloy that is primarily used for total joint
prostheses. It should be noted that stainless steel + pure titanium
is also viewed as unsafe because the corrosion resistance of pure
titanium and titanium alloys (including Ti-6Al-7Nb) are very similar
and produce nearly equivalent galvanic reactions when coupled with
implant quality stainless steel. The predicted behavior is based on
laboratory experiments and is a first approximation of whether clinical
problems may be experienced.
Mixing of stainless steel implants with unalloyed titanium, titanium
alloy, and cobalt alloy implants should be avoided for implants that are
in contact with each other. This recommendation is consistent with a
critical review of the best available information on the use of dissimilar
biomaterials for orthopaedic applications. The use of mixed metals in
the same bone is not a problem as long as the implants are not in
direct contact with each other.
5. Biocompatibility
In 1974, Desai and Sinkford 29 inserted screw-shaped stainless steel,
gold, and platinum alloy implants into rat femurs. The authors found
the thinnest connective tissue layer at the stainless steel interface after
a 5-week implantation. The stainless steel implants did not provoke an
inflammatory response.
Pfluger 30 in 1980 implanted different materials in rabbit tibia which
included porous and grooved stainless steel, tantalum, and niobium
implants. Histological results between 3-week and 6-month implanta-
tion revealed that all metals were equally biocompatible.
Millar et al. performed a histological study 31 in 1990 that evaluated
the effect of bone tissue reactions to stainless steel and titanium
screws implanted in canine skulls. No significant differences were
observed in the tissue reactions between stainless steel and titanium
screws after 4-, 12-, and 24-week implantation periods.

18
Gerber and Perren 32 developed an embryonic bone culture test to
evaluate metal-related cellular behavior of an extensive array of metals,
including stainless steel. In this series of experiments, implant quality
stainless steel was well tolerated as evidenced by the appearance of
normal cartilage cells near the implant.
Soft tissue reactions around stainless steel and titanium LC-DCP bone
plates in sheep were evaluated by Ungersbock, Pohler, and Perren 33.
A thicker soft tissue capsule layer was observed for the stainless plates
when compared to titanium. However, all implants demonstrated good
biocompatibility with a low number of round cells, mast cells, macro-
phages, and polymorphonucleated leukocytes in the soft tissue
covering the plates.
ASTM F 138 implant quality stainless steel 6 has been successfully used
for human implants for nearly 30 years. The alloy has a well character-
ized level of local biological response and is specified as a control mate-
rial in ASTM F 981 Standard Practice for Assessment of Compatibility
of Biomaterials for Surgical Implants with Respect to Effect of Materials
on Muscle and Bone 34.
The possibility of metal sensitivity reactions must be considered when
evaluating the overall biocompatibility of implant quality stainless steel.
The most common metal sensitivity test for human patients involves
paravertebral patch testing on the skin of the back. The standard aller-
gens include 2.5% nickel sulfate, 0.5% potassium dichromate, and
1% cobalt chloride solutions dispersed in petrolatum. The test patches
remain in situ for 48 hours and the skin reactions are recorded after
48, 72, and 96 hours. Test results reported by S. and G. Hierholzer 35
for 208 human patients who experienced uncomplicated healing with
stainless implants indicated about 4% were allergic to nickel and/or
chromium. Slightly over 10% of 497 patients who had aseptic or septic
complications displayed evidence of metal sensitivity while nickel
accounted for greater than 90% of the allergic reactions.
6. Surface
Electropolishing has emerged as one of the most common surface
treatments for stainless steel implants. The first step in the electropol-
ishing process consists of securing the implants to special fixtures or
loading them into wire baskets. The fixtures or baskets are placed on a
copper bar known as the anode in the middle of the process tank. The
anode is surrounded by one or more stainless steel plates known as the
cathode. An electrical current is applied to the fixtured implants which
are immersed in an acidic solution. The electropolishing process

19
Properties continued

removes a measurable amount of metal from the implant surface at a

controlled rate and produces a very smooth surface. The amount of
metal that is removed is primarily dependent on the applied current
and the immersion time.
The electropolishing process usually includes a pre-cleaning step to
remove oil, grease and loose organic or inorganic surface debris that
may be present from the various manufacturing operations. The actual
electropolishing treatment tends to remove superficial foreign material,
improves the corrosion resistance 36, provides a low friction surface, and
creates a passive film 37 on the implant surface. Various types of foreign
material may include free iron from machining tools, contact films from
various sources, and imbedded particles from surface texturizing opera-
tions. A smooth electropolished surface roughness of around 5 micro-
inch AA (Arithmetic Average) is normally obtained for stainless
implants and this provides a low coefficient of friction. A reduced
coefficient of friction can be an advantage for multicomponent
implants where fretting corrosion is a consideration.
Sulfur content greater than 0.005% can promote surface blemishes on
electropolished stainless steel implants. The manganese sulfides pres-
ent at the surface of the implant will be preferentially attacked during
electropolishing and cosmetic features may be compromised. Uniform
surface appearance is not as problematic when bead blasting or shot
peening are used to produce a textured surface before electropolishing.
Typical implant quality compositions rarely exceed 0.002% sulfur
content and electropolishing problems will be minimized regardless
of whether a smooth or matte finish is desired.
Implants which are not electropolished must be chemically passivated
to restore maximum corrosion resistance. Various nitric acid concentra-
tions and temperatures for the chemical passivation of stainless steel
surgical implants are compiled in ASTM F 86 specification 38.
Surface operations such as electrochemical etching or laser marking
may be used to identify stainless steel implants. Selective nitric acid
repassivation is generally required to improve the corrosion resistance
of the electrochemically or laser marked area.

20
Clinical Features

Biocompatibility
Successful human implantation for over 30 years.
Galvanic corrosion
Stainless steel implants should not be in contact with titanium-based or
cobalt-based implants.
Mechanical
Stainless steel implants have a good combination of strength and
ductility.
Metal sensitivity
A small percentage of patients may be allergic to nickel.
MRI
Starburst or signal void effects may interfere with diagnostic imaging.
Sterilization
Steam autoclave, ETO, gamma radiation, electron beam, and other
methods may be used.
Surface
Electropolishing provides low frictional surface properties.

21
References

1. Laing, P. G., Clinical Experience with Prosthetic Materials:

Historical Perspectives, Current Problems, and Future Directions,
Corrosion and Degradation of Implant Materials, ASTM STP 684,
B. C. Syrett and A. Acharya, Eds., American Society for Testing
and Materials, 1979, p. 202.
2. Peterson, L., Fixation of Bones by Plates and Screws, Journal of
Bone and Joint Surgery, Vol. 29, 1947, pp. 335-347.
3. Blunt, J. W., Jr., Hudack, S. S., and Murray, C. R., Metals and
Plastics in Orthopedic Surgery and General Surgery, Clinical
Congress, American College of Surgeons, New York, 1952.
4. ASTM F 55-65T Standard Specification for Stainless Steel Bar and
Wire for Surgical Implants, American Society for Testing and
Materials, West Conshohocken, PA.
5. ASTM F 56-66 Standard Specification for Stainless Steel Sheet
and Strip for Surgical Implants, American Society for Testing and
Materials, West Conshohocken, PA.
6. ASTM F 138-71 Standard Specification for Stainless Steel Bar and
Wire for Surgical Implants (Special Quality), American Society for
Testing and Materials, West Conshohocken, PA.
7. ASTM F 139-76 Standard Specification for Stainless Steel Sheet
and Strip for Surgical Implants (Special Quality), American Society
for Testing and Materials, West Conshohocken, PA.
8. Pohler, O. and Straumann, F., Characteristics of the Stainless
Steel ASIF/AO Implants, Institute Straumann AG, Waldenburg,
Switzerland, September 1975.
9. ASTM F 1314 Standard Specification for Wrought Nitrogen
Strengthened-22 Chromium-12.5 Nickel-5 Manganese-2.5
Molybdenum Stainless Steel Bar and Wire for Surgical
Implants, American Society for Testing and Materials,
West Conshohocken, PA.
10. ASTM F 1586 Standard Specification for Wrought Nitrogen
Strengthened-21 Chromium-10 Nickel-3 Manganese-2.5
Molybdenum Stainless Steel Bar for Surgical Implants, American
Society for Testing and Materials, West Conshohocken, PA.
11. ASTM F 138 Standard Specification for Wrought 18 Chromium-
14 Nickel-2.5 Molybdenum Stainless Steel Bar and Wire for Surgi-
cal Implants (UNS S31673), American Society for Testing and
Materials, West Conshohocken, PA.

22
12. ISO 5832-1, Implants for Surgery-Metallic materials-Part 1:
Wrought stainless steel, International Organization for
Standardization, Geneva, Switzerland.
13. ASTM A 276 Standard Specification for Stainless Steel Bars
and Shapes, American Society for Testing and Materials,
West Conshohocken, PA.
14. ASTM E 45 Standard Test Methods for Determining the Inclusion
Content of Steel, American Society for Testing and Materials,
West Conshohocken, PA.
15. Mills, K., Davis, J. R., Dieterich, D. A., Crankovic, G. M., and
Frissell, H. J., Metallographic Techniques and Microstructures:
Specific Metals and Alloys, Metals Handbook Ninth Edition:
Metallography and Microstructure, American Society for Metals,
Metals Park, OH, 1985, pp. 284-289.
16. ASTM A 262 Practices for Detecting Susceptibility to Intergranular
Attack in Austenitic Stainless Steels, American Society for Testing
and Materials, West Conshohocken, PA.
17. Disegi, J. A., Magnetic resonance imaging of AO/ASIF
stainless steel and titanium implants, Injury, AO/ASIF Scientific
Supplement, Volume 23, Supplement 2, 1992, pp S1-S4.
18. Carpenter Technology Corporation Alloy Data, Biodur 316LS
Stainless, Medical Implant Alloys, Carpenter Technology Corp.,
Reading, PA, 2/95.
19. ISO 6892 Metallic Materials-Tensile Testing, International
Organization for Standardization, Geneva, Switzerland.
20. ASTM F 1350 Standard Specification for Stainless Steel Surgical
Fixation Wire, American Society for Testing and Materials,
West Conshohocken, PA.
21. ASTM F 139 Standard Specification for Wrought 18 Chromium-
14 Nickel-2.5 Molybdenum Stainless Sheet and Strip for Surgical
Implants (UNS S31673), American Society for Testing and
Materials, West Conshohocken, PA.
22. Pohler, O., Failures of Metallic Orthopedic Implants,
Metals Handbook, Ninth Edition, Volume 11 Failure Analysis and
Prevention, American Society for Metals, Metals Park, OH, 1985,
pp 683-688.
23. Shetty, R. H., et al. Metals in Orthopedic Surgery, Encyclopedia
Handbook of Biomaterials and Bioengineering, Part B Applica-
tions, Volume 1, Marcel Dekker, 1995, p. 536.

23
References continued

24. Steinemann, S. G., Corrosion of surgical implants: in vivo and

in vitro tests, Evaluation of Biomaterials, G.D. Winter, J.L. Leray,
and K. deGroot, Eds., John Wiley and Sons Inc., New York, 1980,
pp 11-34.
25. Sheehan, J. P. et al., Study of Stress Corrosion Cracking Suscepti-
bility of Type 316L Stainless Steel In Vitro, Corrosion and Degra-
dation of Implant Materials: Second Symposium, ASTM STP 859,
A. C. Fraker and C. D. Griffin, Eds., American Society for Testing
and Materials, Philadelphia, 1985, pp 57-72.
26. Brown, S. A., and Merritt, K., Fretting Corrosion of Plates and
Screws: An In Vitro Test Method, Corrosion and Degradation of
Implant Materials: Second Symposium, ASTM STP 859, A. C.
Fraker and C. D. Griffin, Eds., American Society for Testing and
Materials, Philadelphia, 1985, pp 105-116.
27. Ruedi, T. P., Titan und Stahl in der Knochenchirurgie, Heft 123,
Springer-Verlag, 1975.
28. Barbosa, M. A. Corrosion Mechanisms of Metallic Biomaterials,
Biomaterials Degradation: Fundamental Aspects and Related
Clinical Phenomena, Chapter 9, M. A. Barbosa (Ed.), Elsevier
Science Publishers BV, The Netherlands, 1991, pp 250-253.
29. Desai, R. J. and Sinkford, J. C., Tissue response to intraosseous
implants in albino rats, Oral Surgery, Oral Medical Oral Pathology,
Volume 37, 1974, p. 26.
30. Pfluger, G., et al., Bone reactions to porous and grooved stainless
steel, tantalum, and niobium implants, Biomaterials, G. D. Win-
ter, D. F. Gibbons, and H. Plenk Jr., (Eds.), 1980, pp 45-50.
31. Millar, B. G., Frame, J. W., and Browne, R. M., A histological
study of stainless steel and titanium screws in bone, British Jour-
nal Oral Maxillofacial Surgery, Volume 28, 1990, pp 92-95.
32. Gerber, H. and Perren, S. M., Evaluation of Tissue Compatibility
of in vitro Cultures of Embryonic Bone, Evaluation of Biomateri-
als, G. D. Winter, J. L. Leray, and K. deGroot, (Eds.), 1980,
pp 307-314.
33. Ungersbock, A., Pohler, O. E. M., and Perren, S. M., Evaluation
of soft tissue reactions at the interface of titanium limited contact
dynamic compression plate implants with different surface treat-
ments: an experimental sheep study, Biomaterials, Vol. 17, No. 8,
1996, pp 797-806.

24
34. ASTM F 981 Standard Practice for Assessment of Compatibility of
Biomaterials for Surgical Implants with Respect to Effect of Materi-
als on Muscle and Bone, American Society for Testing and Materi-
als, West Conshohocken, PA.
35. Hierholzer, S. and Hierholzer, G., Internal Fixation and Metal
Allergie, Thieme Medical Publishers, New York, 1992.
36. Irving, C. C., Jr., Electropolishing Stainless Steel Implants,
Corrosion and Degradation of Implant Materials: Second
Symposium, ASTM STP 859, A. C. Fraker and C. D. Griffin, (Eds.),
American Society for Testing and Materials, Philadelphia, 1985,
pp 136-143.
37. ASTM A 967 Standard Specification for Chemical Passivation
Treatments for Stainless Steel Parts, American Society for Testing
and Materials, West Conshohocken, PA.
38. ASTM F 86 Standard Practice for Surface Preparation and Marking
of Metallic Surgical Implants, American Society for Testing and
Materials, West Conshohocken, PA.

25
Glossary

ALLOY. Metallic substance composed of two or more elements, at

least one of which is a metal.
ALLOYING ELEMENT. An element added to and remaining in a
metal that changes the metallic structure and properties.
ANNEALING. Metal-softening operation in which the alloy is heated
to and held at a specific temperature, followed by cooling at a con-
trolled rate.
ANODIC REACTION. Oxidation reaction that produces electrons at
the anode of an electrochemical cell.
ARGON OXYGEN DECARBURIZATION (AOD). Stainless steel
refining process in which a mixture of argon and oxygen gas is injected
through the molten alloy to reduce the carbon content and to remove
impurities.
ASEPTIC. Free from septic matter.
AUSTENITE. The normal face-centered cubic crystalline structure of
implant quality stainless steel with good formability and nonmagnetic
properties.
BILLET. Semifinished round or square product that has been hot
worked by forging, rolling, or extrusion.
BLOOM. Semifinished rectangular hot rolled product that is usually
larger than a billet.
BODY-CENTERED CUBIC. A unit cell which consists of atoms
arranged at cube corners with one atom at the center of the cube.
BRITTLENESS. The tendency of a material to fracture without first
undergoing significant permanent deformation.
CATHODIC REACTION. Reduction reaction that consumes elec-
trons at the cathode of an electrochemical cell.
COLD WORKED MICROSTRUCTURE. A microstructure resulting
from cold working the material.
COLD WORKING. Permanently deforming a metal or alloy at room
temperature to increase its strength.
DESCALING. Chemically or mechanically removing the thick oxide
layer that is formed on alloys during high temperature processing.
DELTA FERRITE. A secondary magnetic phase that can be present in
austenitic stainless steel but is not permitted in implant quality stainless
steel.
DUCTILITY. The ability to permanently deform before fracturing.

26
ELECTRODE. Cylindrical metal ingot that is suitable for remelting.
ELECTROPOLISHING. Metal finishing process in which a smooth,
highly polished surface is produced by an electrochemical anodic reac-
tion in an electrolytic cell.
ELECTROSLAG REMELTING (ESR). Consummable electrode
melting process in which an electrode is melted into an ingot by the
passage of electric current through a conductive slag layer at the
surface of a mold.
ELONGATION. A term that describes ductility by measuring the
amount of extension that a material undergoes during tensile testing.
ENDURANCE LIMIT. The maximum stress below which a material
can presumably endure an infinite number of stress cycles.
EXTRA HARD. Metalworking term used to describe material that
has been subjected to a high amount of cold work.
FATIGUE. The phenomenon leading to fracture under repeated or
fluctuating stresses having a maximum value less than the ultimate
tensile strength of the material.
FATIGUE LIFE. The number of cycles of stress or strain of a specified
character that a given specimen sustains before failure of a specific
nature occurs.
FATIGUE STRENGTH. The maximum stress that can be sustained
for a specified number of cycles without failure, the stress being
completely reversed within each cycle unless otherwise stated.
FRETTING CORROSION. An accelerated form of corrosion that
can occur when the protective passive film at the surface of a metal or
alloy is mechanically disrupted in a corrosive environment. The relative
motion of the underside of a bone screw head with the contact
surface of a bone plate is a typical example.
GALVANIC CORROSION. Corrosion associated with the current of
a galvanic cell consisting of two dissimilar conductors in an electrolyte.
GRAIN SIZE. A measure of the area or volume of grains in a metal
or alloy.
HOT WORKED MICROSTRUCTURE. Microstructure resulting
from hot working the material.
HOT WORKING. Permanently deforming a metal or alloy at an
elevated temperature that is usually above the recrystallization
temperature.

27
INCLUSION. A particle of foreign material in a metallic microstruc-
ture that is usually considered undesirable.
INGOT. A metal casting that is suitable for remelting or hot working.
LONGITUDINAL. Parallel to the principal direction of hot or cold
working.
MACROPHAGE. A cell having the ability to ingest bacteria and
foreign particles.
MARTENSITE. Generic term for an acicular microstructure formed
by a diffusionless phase transformation. A martensitic stainless steel
microstructure is magnetic.
MAST CELL. Connective tissue cell.
MICROCLEANLINESS. A relative measure of the amount of non-
metallic inclusions that are present in a metal or alloy.
MICROSTRUCTURE. The structure of metals and alloys as revealed
by microscopic examination of specimens.
MODULUS OF ELASTICITY. A measure of the stress per unit strain
in the elastic region before permanent deformation occurs.
PARAVERTEBRAL. Alongside or near the vertebral column.
PASSIVATION. The process of changing the chemical activity of a
metallic surface to a less reactive state, usually to increase the corrosion
resistance.
PASSIVE FILM. Protective surface film formed on a metal or alloy
as a result of a passivation reaction.
PATHOGEN. A microorganism or substance capable of producing
disease.
PERMEABILITY. A generic term which is the ratio of the induction
to the magnetic force under specific magnetizing conditions.
PICKLING. Chemical removal of the thick oxide layer that is formed
on metals and alloys during high temperature processing.
PITTING CORROSION. A corrosion process that forms small sharp
cavities in a metallic surface.
POLYMORPHONUCLEATED LEUKOCYTE. White blood cell
with a nucleus composed of two or more lobes or parts.
RECRYSTALLIZATION. A change from one crystal structure to
another that occurs during heating or cooling through a critical
temperature range.

28
REDUCTION OF AREA. The difference, expressed as a percentage
of original area, between the original cross-sectional area of a tensile
test specimen and the minimum cross-sectional area measured after
complete separation.
ROUND CELL. Spherical or globular shaped cell.
SENSITIZATION. A condition of being made sensitive to a specific
substance such as a protein, pollen, or metal.
SEPTIC. Pertaining to pathogenic organisms or their toxins.
SIGMA PHASE. A hard, brittle, nonmagnetic secondary phase with
a tetragonal crystal structure that can be present in austenitic stainless
steel.
STAINLESS STEEL. An iron base alloy that contains at least 10%
chromium as the principal alloying element.
STRAIN. Change in length per unit length in the direction of the
applied stress.
STRAIN RATE. The time rate of straining for the usual tensile test.
STRESS. Force per unit area.
STRESS CORROSION CRACKING. Failure of metals and alloys by
cracking under combined action of corrosion and either residual and/or
applied stress.
TRANSVERSE. Perpendicular to the principal direction of hot or cold
working.
ULTIMATE TENSILE STRENGTH. In tensile testing, the maximum
load at fracture divided by the original cross-sectional area.
VACUUM ARC REMELTING (VAR). Consummable electrode
melting process in which an electric arc is used to remelt an electrode
into an ingot in a vacuum chamber.
VACUUM INDUCTION MELTING (VIM). A process for melting
and refining metals in which the metal is melted inside a vacuum
chamber by induction heating.
WROUGHT. A metal or alloy that has been shaped by pressing, forg-
ing, rolling, or some other elevated temperature deformation process.
YIELD STRENGTH. In tensile testing, the stress at which the stress
to strain ratio exhibits a specified deviation, usually designated as 0.2%
offset.

29
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