Importance

of

Corrosion

Study

in

of

with the aggressive body fluid, they

Biomedical

often fail and finally fracture due to

Materials.

corrosion. The corrosion behavior

of various implants and the role of

Nweke Kenechukwu Chiemelie

the surface oxide film and the

Metallurgical

corrosion products on the failure of

and

Materials

Engineering, University of Nigeria

implants

are

discussed.

Surface

Nsukka. (2010/170291)

modification of implants, which is

considered to be the best solution

Abstract:

to

combat

corrosion

to

In the area of materials

enhance

the

science, corrosion of biomaterials is

implants

and

of

as

human beings is dealt in detail and

biomaterials are required for the

the recent advances in the coating

survival

techniques which make use of the

paramount
of

suffering
diseases,

importance

the

human

beings

from

acute

heart

arthritis,

osteoporosis

superior

life

and

span

of

the

longevity

of

the

properties

of

nanomaterials that lead to better

and other joint complications. The

mechanical

present article discusses various

improved biocompatibility are also

issues associated with biological

presented.

corrosion

of

different

kinds

properties

and

of

implants used as cardio stents,

Keywords:

orthopedic and dental implants. As

biocorrosion, stainless steel, cobalt

the

these

chromium, titanium, titanium alloy,

implants are manifold starting from

magnesium, composites, polymer,

metallic materials such as stainless

failures,

steel

modification,

materials

(SS),

titanium
bioceramics,

used

cobalt
and

for

chromium,
its

composites

alloys,
and

polymers are in constant contact

INTRODUCTION

oxide

Biomaterials,

layer,
cardio

dental and orthopedics.

surface
vascular,

The

field

of

need for biomaterials was acutely

the

felt and in the recent context of

mankind as the very existence and

global terrorism, this field assumes

longevity

less

much more significance. The field

fortunate human beings, who even

of biomaterials is not new and as

at the time of birth are born with

early

congenital heart disease and also

Egyptians and Romans have used

for

who

linen for sutures, gold and iron for

to

dental applications and wood for

increase their life span. The aged

toe replacement but with very little

people need the help of geriatric

knowledge about the problem of

physicians for several ailments as

corrosion. Nylon, Teflon, silicone,

the parts of the human system

stainless steel and titanium were

have

expected

some of the other materials which

tasks for long years and have

were put into use after World War

become worn out. Arthritis is one of

II.

the major illnesses generally faced

better

by the aged and even at times

advancements in the knowledge on

young people are also affected by

materials as well as on surgical

this disease and it impairs the life

procedures,

of

to

assumed greater significance and

immobility and unbearable pain.

bioimplants are commonly used in

However, the cause of this disease

dentistry, orthopedics, plastic and

remains unknown even today in

reconstructive

spite

ophthalmology,

cardiovascular

surgery,

neurosurgery,

immense

biomaterials

importance
of

the

require

of

some

aged

performed

of

of

the

implants

their

affected

leading

tremendous

advancements.
diseased

for

population

biomedical

those

is

scientific

Apart

Currently,

years

the

diagnostic

back

availability
tools

implantology

dynamic people like sportspersons

experimental

often need replacements due to

veterinary medicine (Fig. 1).

excessive

strain.

Especially after the world wars, the

the

of
and

has

surgery,

immunology,

and

young

4000

and

fracture

people,

from

as

histopathology,
surgery,

and

works at the laboratory were first

tested on animals which led to the
birth of the ultimate biomaterials
that could be accepted by the
human

system.

foremost

The

requirement

first

and

for

the

choice of the biomaterial is its

acceptability by the human body.
The implanted material should not
cause

any

adverse

effects

like

allergy, inflammation and toxicity

either immediately after surgery or
under post operative conditions.
Various classes of materials such

Secondly,

as

possess

metals,

ceramics

alloys,

and

polymers

sufficient

should

mechanical

have

strength to sustain the forces to

been widely used to fabricate the

which they are subjected so that

bioimplants.

they do not undergo fracture and

encounter
environments

composites

biomaterials

These

implants

different

biological

of

very

different

more

importantly,

bioimplant

should have very high corrosion

physico-chemical nature and their

and

interaction with the tissues and

corrosive body environment and

bones

problem.

varying loading conditions, apart

was

from fatigue strength and fracture

completely lacking in the early

toughness. A biomaterial should

years of human existence and the

remain intact for a longer period

credit for the origin and evolution

and should not fail until the death

of todays bioimplants are due to

of the person. This requirement

Harold Ridley, Paul Winchell, Per-

obviously

Ingvar Branemark, Otto Wichterle,

service period of from 15 to 20

John Charnley and others. Their

years in older patients and more

is

Scientific

complex
knowledge

wear

resistance

demands

in

highly

minimum

than 20 years for younger patients.

interested reader can go through

The success of a biomaterial or an

them to gain mastery over this

implant is highly dependent on

subject. This article is divided into

three

the

seven sections; section 1 discusses

properties (mechanical, chemical

the reasons which lead to the

and tribological) of the and (iii) the

corrosion

health condition of the recipient

biological

and

the

corrosion behavior of the surface

used

oxide layer formed on the implants

materials that were selected based

and the reasons for the failure of

on

criteria

the implants are described in detail

though function well in the human

in sections 2 and 3 respectively.

system are still found to generally

The

fail within a period of about 12-15

conventional as well as the recently

years,

developed alloys are discussed at

major

the

factors

(i)

competency

surgeon.

The

above

currently

mentioned

which

of

leads

to

revision

of

bio-implants

environment.

corrosion

functionality of the system. The

Section 5 is devoted to a discussion

reasons

are

on the corrosion of cardiovascular,

includes

dental and orthopedic implants.

mechanical, chemical, tribological,

The prevention of corrosion by

surgical,

and

appropriate coating techniques is

biocompatibility issues. Out of all

dealt with in section 6. The current

these issues, the failure of an

and

implant

regard

manifold

failure

which
manufacturing

due

to

corrosion

has

future
to

4,

of

length

their

Section

The

surgery in order to regain the

for

in

behavior

in

whereas,

developments
the

corrosion

with
of

remained as one of the challenging

biomedical implants are discussed

clinical problems. This important

in the final section 7.

field of research, over the years,

has been discussed at length by

1. WHY METALS CORRODE IN

several authors in the form of

HUMAN BODY?

books [1-10] and comprehensive

Corrosion, the gradual degradation

review articles [11-15] and the

of

materials

by

electrochemical

attack

is

of

concern

formed by the electrons on the

metallic

surface and excess cations in the

implant is placed in the hostile

solution. In addition, proteins that

electrolytic

the

are absorbed on the surface are

human body. The implants face

also found to reduce the diffusion

severe

of oxygen at certain regions and

particularly

great

when

environment

corrosion

of

environment

which includes blood and other

cause

constituents of the body fluid which

those regions. Hydrogen which is

encompass

formed by cathodic reaction acts as

like

several

water,

proteins,

constituents

sodium,

plasma,

chlorine,

amino

acids

preferential

corrosion

at

a corrosion inhibitor, however, the

presence

of

bacteria

seems

to

along with mucin in the case of

change this behavior and enhance

saliva [16]. The aqueous medium in

corrosion

the human body consists of various

hydrogen present in the vicinity of

anions such as chloride, phosphate,

the implant. Changes in the pH

and bicarbonate ions, cations like

values also influence the corrosion.

Na+, K+, Ca2+, Mg2+ etc., organic

Though, the pH value of the human

substances of low-molecular-weight

body is normally maintained at 7.0,

species

this value changes from 3 to 9 due

as

well

highmolecular-

as

relatively

weight

polymeric

to

several

by

absorbing

the

causes

such

as

imbalance

in

the

components, and dissolved oxygen

accidents,

[17, 18]. The biological molecules

biological system due to diseases,

upset

the

infections and other factors and

corrosion reactions of the implant

after surgery the pH value near the

by consuming the products due to

implant varies typically from 5.3 to

anodic or cathodic reaction.

5.6. In spite of the fact that most of

Proteins can bind themselves to

the materials used are protected

metal ions and transport them

by the surface oxide layers from

away from the implant surface

the environmental attack, there is

upsetting the equilibrium across

clinical evidence for the

the

equilibrium

of

the surface double layer that is

release of metal ions from the

to tribocorrosion. Fretting results in

implants and this leaching has

the rupture of protective oxide

been

layer,

attributed

to

corrosion

initiation

of

cracks

and

process. It has been well accepted

formation of reactive metal atoms

that the tolerable corrosion rate for

on the surface that are susceptible

metallic implant systems should be

to corrosion [23]. In order to limit

about 2.5 x 10 4 mm/yr, or 0.01

further oxidation, initially formed

mils/yr [19]. The most common

passive films must have certain

forms of corrosion that occur are

characteristics; i) non - porous ii)

uniform

atomic structure that will limit the

corrosion,

galvanic

and

intergranular,

stress

corrosion

migration of ions and electrons

fatigue

across the metal oxide - solution

new

interface and iii) high abrasion

materials are continuously being

resistance. Hence, when a material

developed

is

cracking,

pitting

corrosion.

Even
to

and
though

replace

implant

developed

for

implant

materials used in the past, clinical

application, it should not only be

studies show that these materials

subjected

are also prone to corrosion to a

screening test, but also has to be

certain

tested

physical

extent

[20].

The

characteristics

two
which

to

for

different

basic

its

corrosion

behaviour

conditions

under

such

as

determine implant corrosion are

reciprocatory wear, fretting, stress

thermodynamic forces which cause

corrosion etc depending up on their

corrosion either by oxidation or

applications.

reduction reaction and the kinetic

standards

barrier such as surface oxide layer

resistance of these materials under

which physically prevents corrosion

different conditions. The commonly

reactions [20-22]. In some cases

used standards for testing different

though the material will not fail

corrosion processes are given in

directly due to corrosion, it is found

Table 1

to fail due to accelerated processes

such as wear and fretting leading

for

There

are

testing

ASTM

corrosion

the release of metallic ions and the

behavior

of

the

surface

oxide

changes with the release of ions.

Further, the composition of the
surface

oxide

film

changes

according to reactions between the

surfaces of metallic materials and
. Corrosion is accelerated in the

living

presence

also

concentration of dissolved oxygen,

simultaneous corrosion and wear

inorganic ions, proteins, and cells

are

may

of

often

wear

and

encountered

in

tissues.

accelerate

Even

the

low

metal

ion

biomedical implants. Dearnley et

release. In addition, the dissolution

al. have evaluated the corrosion

of surface oxide film due to active

behavior of the scratched coated

oxygen

specimens to determine the wear

reported

accelerated corrosion behavior of

time of the surface oxide film after

the coatings and also suggested a

disruption also decides the amount

methodology

of

to

measure

the

species

has

[26].

ions

The

also

been

regeneration

released.

Tissue

simultaneous corrosion and wear of

compatibility, the prerequisite for

a material [25]. However it is

an implant is basically determined

important to note that there are no

by the nature of the reactions

standards available to test the

which take place at the initial

tribocorrosion

stages after implantation and thus

behavior

of

the

implants.

the success of the implant depends

on

2.

SURFACE OXIDE FILM

METALLIC

MATERIALS

metallic

oxide

film

materials

reactions

taking

place

ON

between the surface of metallic

IN

materials and living tissues soon

BIOLOGICAL ENVIRONMENT
Surface

the

after the fixation of the implant.

formed

on

Surface

oxide

plays

an

metallic

materials

important role as an inhibitor for

important

films

role,

present

play
not

a
only

on
very
for

corrosion resistance but also for

tissue compatibility. Therefore, as
pointed

out

by

Kasemo

and

Lausma [26], it is important to

analyze the surface characteristics
of these materials when discussing
the issues of corrosion and tissue
compatibility. Biomedical implants
should be subjected to both in vitro
and

in

vivo

studies

for

their

applications. In vitro studies which

are performed in simulated body
condition give an overview of the
behavior of the material under the
given condition and obviously it
cannot be taken as the final test to
recommend

material

as

an

implant. The in vivo tests which are

performed

using

animal

models

whereas the corrosion resistance

for dental materials is evaluated
using

synthetic

saliva

whose

constituents could be seen in Table

4.

evaluate the actual performance of

the materials and these tests are
required in order that it is approved
by

FDA

(Food

Administration,

and

USA).

In

Drug
vitro

corrosion studies on orthopaedic

biomaterials are
carried out either in Hanks solution
or

Ringer

solution

whose

constituents are given in Tables 2

and 3 respectively,

It should be mentioned here that

various

compositions

have

also

been suggested which are close to

the natural saliva [27]. Three of the

metallic biomaterials is given in

existing

Table 5.

saliva

substitutes

are

xialine 1, xialine 2 and saliveze,

where xialine 1 and xialine 2 are
based on xanthan gum and the
saliveze

is

based

on

carboxymethylcellulose.

Main

constituents of artificial saliva are

Mg2+, K+, Na+, Cl-, SCN-, NH4 +,
Ca2+, CO3tot (where, [CO3]tot =
[CO3 2] + [HCO3 ]), and the pH
is near neutral. In addition to these
ions,

presence

organic

of

fraction

of

such

as

compounds

glycoprotein, have been reported in

the saliva and it plays an important
role in maintaining the viscosity
which, in turn, affects the diffusion
of various ions.
However, its effect on the corrosion
of

biomaterials

remains

to

be

understood [28]. The oxide film

which inhibits the dissolution of
metal ions is not always stable in
the human body and hence a
thorough

understanding

of

the

behavior of the oxide film in in vivo

condition is essential to have a
better

insight

of

the

corrosion

phenomenon. The analysis of the

surface

oxide

film

on

various

Table 2. Composition of Hanks

Solution
When the surface oxide film
of a metallic material is disrupted,
corrosion proceeds and metal ions
are released continuously unless
the

film

is

interactions
physiological

regenerated.
between
medium

and

The
the
the

material play a decisive role on the

reformation of the oxide layer and
the time taken for the same. The
time taken for repassivation which
is also termed as regeneration time
is different for various materials
used. The corrosion rate following
the disruption and the quantity of
released metal ions depend up on
the above said regeneration time.
Regeneration time taken to form

surface

oxide

films

for

various

alloys is illustrated in Fig. (2).

and

titanium

containing

oxyhydroxide

titanium

phosphate.

Calcium and phosphate ions are

also adsorbed to the film after
regeneration,
phosphate

or

phosphate

are

and

calcium

calcium

titanium

formed

on

the

From these observations, it

outermost surface. In Ti-6Al-4V also

is found that the regeneration time

calcium phosphate was observed

is longer in stainless steel and

on

shorter in Ti-6Al-4V, an alloy which

regenerated in Hanks solution and

is well known and widely used for

on

orthopedic applications, indicating

without calcium is formed on Ti-

a fact that larger number of metal

56Ni,

ions being released from stainless

biomaterials. Thus the composition

steel compared to the latter, which

of

brings out one of the superior

interaction with the environment is

qualities possessed by this alloy,

highly

apart from its other advantageous

constituents of the material used.

properties. The repassivation rate

The stability of the surface oxide

of Ti in Hanks solution is found to

layer in 316L SS as well as in Ni-Ti

be slower than that in saline and

is not very high and the possibility

remains uninfluenced by the pH of

of metal ions being released is

the

greater

solution.

In

addition,

the

the

surface

other

hand

Ti-Zr

surface

oxide

only

and

oxide

when

phosphate
Zr

layer

dependent

film

based
and

on

compared

its
the

to

surface oxide film regenerated on

conventional alloys such as Co-Cr

Cp Ti in Hanks solution contains

and Ti-6Al- 4V. Hence, in general a

phosphate ions in the outer layer.

coating given on the implants is

Phosphate ions are preferentially

preferable as it will reduce the

filled up during regeneration of

corrosion rate.

surface oxide film on titanium and

the film consists of titanium oxide

Fig.

(2).

Regeneration time of

surface oxide films for various

alloys.

[Ref:

Hanawa

due

to

various

biomaterials,

whereas Table 7 shows the types of

T.

corrosion

in

Reconstruction and regeneration of

materials.

The

surface

Table

amply

oxide film on metallic materials in

possible

hazardous

biological environments.

associated

with

Corrosion Rev 2003; 21: pp. 2-3]

implant material. The release of

the

conventional

contents

of

illustrate
the

the
the

effects
corroded

corrosion products will obviously

3.

EFFECT

OF

CORROSION-

lead to adverse biological reactions

FAILURE OF IMPLANTS

in the host, and several authors

The reaction of the metallic ions

have

that leaches away from the implant

concentrations

due to corrosion in the human body

particles in the tissue near the

affects

biological

implants and other parts of the

parameters. As a material starts to

human body such as kidney, liver

corrode, the dissolution of metal

etc. [29, 30]. In spite of the fact

will lead to erosion which in turn

that

will eventually lead to brittleness

evidence to show the slow release

and fracture of the implant. Once

of metallic ions due to corrosion,

the material fractures, corrosion

the discoloration of the surrounding

gets accelerated due to increase in

tissue

the amount of exposed surface

reactions clearly indicate that this

area and loss of protective oxide

is due to corrosion of implants [31].

layer. If the metal fragments are

Cobalt-chromium alloy which is a

not

commonly

several

surgically

extracted,

further

reported

there

and

increased
of

is

no

the

used

corroded

histological

foreign

body

biomaterial

dissolution and fragmentation can

consists of the elements cobalt,

occur,

in

chromium, nickel and molybdenum.

inflammation of the surrounding

It is felt that the corrosion of

tissues.

the

cobalt-chrome in the wet and salty

effects of corrosion in human body

surroundings of the human body,

which
Table

may
6

result

illustrates

releases toxins into the body which

orthopedic applications. J Fail Anal

in turn

Prevent 2004; 4(3): p. 17].

Aksakal et al. investigated

Table 5. Analysis of the Surface

failed implants made of titanium

Oxide Film on Various Metallic

alloy Ti-6Al-4V and 316L SS that

Biomaterials

were

Metallic

Biomaterial

Surface

removed

from

several

patients [32]. The failure analysis

Oxides Surface Analysis

studied

leads to the formation of cancerous

microscope (SEM) is represented in

tumors. Though the number of

Fig. (3). From the analysis it was

tumors near the implant formed

evident that the failure of femoral

may be less, there is a possibility

titanium

plates

that many could exist at other

through

corrosion

parts of the human body due to the

was promoted by the presence of

released

intense

ions.

Hence

there

is

using

scanning

localized

has

electron

occurred

fatigue

which

corrosion

and

always a need to develop new and

intergranular cracking. In addition,

safer

corrosion

materials

extremely

high

which

have

corrosion

resistance.

fatigue

and

fretting

corrosion have also been observed

in bone plates and screws at the
bone-stem,

Table 6.

and

stem-cement

interfaces of modular hip implants.

The failure of stent device due to
stress corrosion fatigue is a long
term problem and this failure has
been

attributed

to

the

weak

surface of the implant [33]. This

stress

corrosion

cracking

in

biomedical implants can lead to

[Ref: Aksakal B, Yildirim S, Gul H.

loss of structural integrity of the

of

implanted device and its functions.

various implant materials used in

Thus these complications lead to

Metallurgical

failure

analysis

disintegration of the implant [34]. It

of

has been found that this dissolution

chance

of metal ions can be reduced by

carbide that generally results in

suitable

inorganic

intergranular corrosion. Lowering of

coatings, such as hydroxy-apatite

the carbon content also makes this

(HAP) coating with some binders,

type

and this can lead to delay in

corrosion-resistant

corrosion

bearing

biocompatible

and

wear

and

also

less

carbon
of

of

decreases

forming

stainless

the

chromium

steel
to

solutions

more

chlorinesuch

as

minimize the loosening of implants

physiological saline in the human

from bone [35]. Thus the only

body [4]. However stainless steel is

solution to impede corrosion is by

susceptible to localized corrosion

choosing better quality materials

by chloride ions and reduced sulfur

with appropriate coating.

compounds [37]. The presence of

micro

4.

CORROSION

OF

CONVENTIONAL ALLOYS
The

commonly

surface

often

localized

on

leads

damages

metal

to

highly

in

the

surgical

concentration of the electrolytic

implants are usually made from

constituents, pH and oxygen levels

one of the three types of materials:

[38].

austenitic stainless steel, cobalt-

electrochemical behavior of 316L

chromium alloy, and titanium and

SS in the presence of aerobic iron-

its alloys and out of these, 316L

oxidizing

austenitic stainless steel is the

anaerobic sulfate-reducing bacteria

most

(SRB) reveal that the interactions

commonly

used

-organisms

used

implant

Studies

on

corrosion

bacteria

(IOB)

and

and

material as it is cost effective [36].

between the stainless steel surface

4.1. Austenitic Stainless Steels

with

The

employed

bacterial cells and their metabolic

steel alloys are 316 and 316L

products increases the corrosion

grades. ASTM recommends type

damage

316L for implant fabrications for

pitting propagation [39]. In this

the obvious reason that presence

respect,

most

commonly

the

corroded

and

also
the

products,

accelerates
decreasing

antibacterial activity exhibited by

measurement of corrosion potential

different materials is given in the

of cold worked 316L SS and it was

following order gold > titanium >

also

cobalt > vanadium > aluminum >

strength dropped drastically when

chromium > iron [40]. Studies on

the repassivation was suppressed,

retrieved implants show that more

thus, confirming that oxide layer

than 90% of the failure of implants

formation plays a vital role in the

of 316L SS are due to pitting and

determination of the fatigue life of

crevice corrosion attack [41]. These

the

localized

corrosion

and

aggressive corrosive environment

leaching

of

from

[4]. In addition, fretting that occurs

implants necessitate improvement

between implant and bone is also

in the corrosion resistance of the

found to accelerate the fatigue as

currently used type 316L SS by

the repassivation becomes more

bulk

difficult in the presence of fretting.

attacks

metallic

alloying

or

ions

modifying

the

observed

materials

surface [42]. Biomedical materials

Williams,

which

Frazad

are

subjected

to

cyclic

that

al.

fatigue

exposed

Sivakumar

et

the

et

have

to

al.

and

extensively

loading and high stresses in the

reviewed the failure of stainless

presence

steel implants

of

aggressive

environment fail due to fatigue [4,

[1, 36, 43]. The studies which have

6, 26]. Fatigue process is found to

been made by Farzad et al. on the

get further accelerated due to the

stainless steel implants that were

formation of wear debris leading to

fractured

in

fatigue wear. During fatigue there

revealed

interesting

is disruption of the oxide layer and

Several damage mechanisms such

the inability of the material to

as

repassivate immediately exposes

initiation of cracks from these pits,

some region of the metal to the

intergranular

environment leading to corrosion.

inside the crevice, and also stress

The

corrosion

initiation

of

crack

due

to

fatigue was observed during the

crevice

patients

corrosion,
surface
cracking

thighs
results.
pitting,
cracking

(SCC)-like

branched cracks where observed in

the failed implants. But, the main

failure mechanism was determined
to be corrosion fatigue assisted by
crevice corrosion. Apart from the
intensive weakness of the alloy
against the crevice corrosion, the
sulphide

inclusions

assisted

the

corrosion

pits

had

formation
in

the

further
of

the

crevice

regions. These results were further

corroborated by the observations
made by Sivakumar.

Types

of

Corrosion

Conventional

in

Materials

the
Used

for Biomaterial Implants

Type

of

Corrosion

Material

Implant Location Shape of the

Implant
on several patients implanted
with stainless steels. The studies
revealed that the failures are due
to various corrosion mechanisms
and the percentage of corrosion in

various anatomical positions are

illustrated in Figs. (4a, 4b) [41].
These

studies

suggested

that

improvement in the design of the

implants could reduce the number
of

metal-metal

interfaces

or

reduction of the crevice area could

prevent

crevice

addition

to

corrosion.

crevice

In

corrosion,

pitinduced fatigue failure was also

observed in the compression bone
plate

and

corrosion

pit

induced

cracking

in

stress
the

intramedullary nail. The corrosion

failure

not

performance

only
of

impairs

the

the

permanent

implants but also the behavior of

the temporary implants made of
surgical grade type 316L SS [44].
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