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CORROSION OF BIO-MATERIALS

Article  in  International Journal of Materials Science and Engineering · October 2020


DOI: 10.24247/ijmmsejun20203

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International Journal of Metallurgical & Materials
Science and Engineering (IJMMSE)
ISSN (P): 2278–2516; ISSN (E): 2278–2524
Vol. 10, Issue 1, Jun 2020, 21-28
© TJPRC Pvt. Ltd.

CORROSION OF BIO-MATERIALS

MILEEND P. SHARMA
Materials Science and Engineering Department, University of Texas at Arlington, Texas
ABSTRACT

Metalsare used in biomedical implants for several body parts. The in-vivo environment (body fluid) is a very aggressive
towards the metallic surface and corrosion products can be source of local body pain, infections, swelling and failure of
implants. Biocompatibility plays a critical role in selection of the biomaterials. There are many materials available for
selection like ceramics, bio glasses, polymers, metals/alloys but metallic materials are favoured because of their strength
and suitable fabrication properties but their susceptibility to corrosion is of concern for using them as biocomponents.
Most commonly used corrosion resistant metallic biomaterials were developed from Stainless steel 316, Titanium along
with its alloys and Cobalt-Chromium alloys. Protection from corrosion due to passive film plays a crucial role in
corrosion of metallic implants.

KEYWORDS: Corrosion, Metallic Biomaterials, Passivity, Implant & Body Environment

Original Article
Received: Aug 14, 2020; Accepted: Sep 04, 2020; Published: Oct 19, 2020; Paper Id.: IJMMSEJUN20203

1. INTRODUCTION

The tremendously important property of a metallic biomaterial is its “Biocompatibility”. Biocompatibility means
compatibility with existing tissue and they should not produce a toxic or immunologic response when subjected to
body and bodily fluids. In comparison to other implants, metallic implants possess outstanding mechanical effects
for instance high elasticity, machining, wear resistance along with tensile strength. Corrosion of metal in watery
solution was unavoidable except noble metals as metal factors are thermodynamically more stable in their oxide
state, corresponding to their ionization propensity. Due to corrosion, metallic bio-substances lose their surface
function and structural integrity. It quickens their fretting exhaustion, fatigue along with wear, like harm rushes
corrosion. Because of corrosion, alterations in bio environment, like alteration in PH value, sink in dispersed O2, or
modification in chemical elementsetc. can occur. Furthermore, little amounts of released metal ions canaffecta
carcinogenesis and allergic response in the body. Due to this permissible quantity of corrosion in metallic bio-
substances was lesser than that for structural substances for buildings, bridges, etc.[1, 2].

The most widely used metallic material are Stainless steel, Cobalt-Chromium alloys, Titanium as well as
its fusions along with some other metals. When corrosion occurs, flow of electron in metals causes to flow of
electron at the adjacent tissue, thus confusing the nearby tissue. Metal ions may induce problems in the body such
as cytotoxicity, genotoxicity, carcinogenicity, etc. For example, Cr (6+) ions are carcinogenic, while Cr(3+) ions are
not[3]. Potential difference created between body fluid and metal is the major force for the corrosion procedure.
Some defiance in mixture or formation of oxide layer on metal work to preduces the corrosion speed. The metallic
biomaterials used in implants were said to maintain great corrosion defiance due to presence of passive layer on
their surfaces. The rate of corrosion in these metals is very low so they can be called “Self-Protected”. To have
successful implant for a long time the control of corrosion is crucial. There are many different types of corrosion

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22 Mileend P. Sharma

possible in the body, the predominance of the corrosion kindis influenced by the operating circumstances, environment,
construction of inculcate and thermodynamic properties of metal[4].

Figure 1: Biomaterials for Human Application [5].

Common Types of Corrosion in Metallic Biomaterials

In Metallic bio-substances corrosion can be of different types comprising general corrosion and localized corrosion which
contains galvanic corrosion, corrosion exhaustion, pitting, crevice, fretting corrosion, strain-corrosion splitting.

1.1 Galvanic Corrosion

Galvanic corrosion also called as bi-metallic corrosion happens at quickest physical contact with different metal in an
electrolyte for example in serum or body fluid, particularly in an acidic (Low PH)situation following inflammation.
Galvanic corrosion can be uniform or localized. Contact between two dissimilar metals is unavoidable while making
surgical implants. For instance, galvanic corrosion occurs if bone screw as well as bone plate have been created of different
metals or alloys. In many dental implants, the crown is made of various noble metal alloys; so the one which is more noble
might become cathode and the other which is less noble may become anode and the degradation of anode might take place.
However, when the potential difference between the dissimilar metals is quite small, galvanic corrosion might not take
place.[1, 2]

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Corrosion of Bio-Materials 23

1.2 Pitting Corrosion

Pitting was a form of extremely restricted corrosion produced through confined breakdown of passive layer and creation of
cavities in the implant. Pitting usually occurs when halide is present in the environment. Out of all halides, chloride is the
most aggressive ion to pitting and due to the existence of proteins at tissue as well as serum can enhance pitting corrosion.
Studies have shown that metals have characteristic pitting potential. Stable pits are formed at potential noble to pitting
potential. Whereas metastable pits are formed at potential lower than pitting potential, little or no propagation of
pitoccursdue to stable pitting potential[6]. Stainless steel has greater susceptibility for pitting than Ti and Co based alloys
in halide solutions. In implants pitting generally takes place on the underside of screw heads. Resistance to pitting
generally alters with Cr and Mo content[4, 7].

Table 1: Pitting Potential of Biomaterials Determined by Various Methods[7]


Material Electrolyte Pitting Potential, mV Experimental Technique
316L Deaerated, pH-7.4, Hank’s solution, 37C 280 Potentiodynamic
316L 0.9% NaCl solution, 40C 400 Do
316L Do 130 ASTM F746
Coated 316L Deaerated, pH-7.4, Hank’s solution, 449 to 567 ASTM G61
316L Deaerated Hank’s solution 352 Do
316L Deaerated, pH-7.4, Hank’s solution, 37C 280 Do
316L Artificial saliva at 40 C 400 ASTM G61
316 Hank’s solution, at 37C 350 to 400 ASTM G61
Ti–6Al–4V Hank’s solution, at 37C >1000 Do
Ti–6Al–4V Deaerated Hank’s solution, 37C 1900 Do
Co–Cr Deaerated Hank’s solution, 37C 650 Do
Ni–Ti 0.9% NaCl at 40C 100 to 200 ASTM F746
Ni–Ti 0.9% NaCl at 40C 400 ASTM G61
Ni–Ti Artificial saliva at 40C ~ 1000 ASTM G61
Ni–Ti Hank’s solution at 37C ~ 650 ASTM G61

1.3 Crevice Corrosion

Crevice corrosion one kind of restricted corrosion also is associated to microstructure of the inculcate, and itgenerally
occurs in narrow crevices present on the surface of metal because of limited transfer of mass. It can occur within a metal
with metal crackalong with metal with non-metal crack. The reduction of PH, depletion of oxygen and increase innumber
of Cl- ions were the two vital elements in the origination of the fissure corrosion. Such change in the environment causes
the de-passivation of the metal in the crevice. Stainless steel was the major vulnerable out of the blend group considered
here to fissure-persuaded restricted corrosion. At elevated temperatures crevice corrosion of Ti in chloride containing
solutions takes place. In in-vivo environment such are temperature are not seen. For metallic biomaterials, crevice
corrosion may happen on mating surfaces, for example in interface of head-stem in hip joints along with interface of
screw-hole at bone plates.[4, 8]

1.4 Corrosion Fatigue

Corrosion fatigue is the failure of metals due to fracture that happens because of merged interaction of cyclic loading as
well as electrochemical reactions. It is important for metals in cyclic motion applications or load bearing surgical implants.
If the metal was revealed to corrosive surroundings, the collapse might happen in lesser amount of loads as well as
following a short duration. Resistance of corrosion exhaustion was associated to beginning of crevice also techniques of

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24 Mileend P. Sharma

the crack growth. If corrosion pits are present, they can induce fatigue to develop. Failures that are of mechanical origin in
orthopaedic implants are commonly due to corrosion fatigue. Some researchers indicated that heat treatments and nitrogen
implantation can help to raise the corrosion exhaustion in the metallic inculcates.[8, 9]

1.5 Fretting Corrosion

Fretting/Tribocorrosion was well-described as conjoint action of corrosive attack and mechanical wear on the surface of
the material. Fretting corrosion occurs when there is a relative movement or slight oscillation occurs between two differing
surfaces for instance the bone plate and screw head of the prosthetic devices. Even in absence of corrosive environment,
fretting can occur. It is known that passive layer protects the biomedical implant, but due to fretting corrosion the passive
layer is repetitively and locally broken. Thus, bare metal surface, which is more susceptible to corrosion is exposed
repetitively to the environment. Surface alteration techniques like plasma surface alloying, plasma ion nitriding, nitrogen
ion implantation and may increase the fretting resistance of biomaterials.[2, 10]

The Body Environment

The body environment is an aggressive to the metals and alloys implanted inside. The body contains 50% to 70% water of
its total mass. Corroded metals may interact with body fluids, various cells and enzymes that can induce allergy and
toxicity and ultimately failure of implant. The corrosion of metallic biomaterials canlibe rate undesirable metal
ions/corrosion product that were non bio-compatible, or it might reduce the implant life and may reduce human life. The
main two cathodic reaction in corrosion in general in-vivo environment are oxygen evolution reaction (OER)along with
hydrogen evolution reaction (HER). The HER in acid solution is:

2H+ + 2e- → H2,

whereas in alkaline solution it is:

2H2O + 2e- → H2 +2(OH)-.

The OER in acidic solution is:

O2 + 4H+ + 4e- → 2H2O,

Whereas in the alkaline solution it is:

4OH- → O2 + 4e- + 2H2O [11].

Since corrosion testing cannot be done inside a body, the environment is recreated inside in vitro condition.
Various solutions are available for testing like Ringer’s mixture, Hank’s compound, artificial saliva[5, 8]. Their
composition is given in the table below.

Table 2: Compositions of Various Simulated Body Fluids.[12]


Component PBS (g.L-1) Ringer’s (g.L-1) Hank’s (g.L-1)
NaCl 8.00 8.60 8.00
CaCl2 - 0.33 0.14
KCl 0.20 0.30 0.40
MgCl2.6H2O - - 0.10
MgSO4.7H2O - - 0.10
NaHCO3 - - 0.35
NaH2PO4 1.15 - -
Na2HPO4.12H2O - - 0.12

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Corrosion of Bio-Materials 25

KH2PO4 0.20 - 0.06


Phenol red - - 0.02
Glucose - - 1.00

Table 3: Composition if Different Artificial Saliva.[13]


Components Xialine 1(g · L -1 ) Xialine 2 (g · L -1) Saliveze (g · L-1)
Xanthan gum 0.92 0.18 -
Sodium carboxymethylcellulose - - 10
Potassium chloride 1.2 1.2 0.62
Sodium chloride 0.85 0.85 0.87
Magnesium chloride 0.05 0.05 0.06
Calcium chloride 0.13 0.13 0.17
Dipotassium hydrogen orthophosphate 0.13 0.13 0.80
Potassium dihydrogen orthophosphate - - 0.30
Sodium fluoride - - 0.0044
Sorbitol - - 29.95
Methyl p-hydroxybenzoate 0.35 0.35 1.00
Spirit of lemon - - 5 ml

There are many different standards used for evaluating corrosion defiance of substances beneath diverse
situations. One of the most common is ASTM (American Society for Testing and Materials). The most used ASTM norms
for evaluating the distinct corrosion procedures of metallic biomaterials were shown in below table.

Table 4: Standards for Testing Corrosion Resistance of Biomaterials.[14]


Standard Specifications
ASTM Standard Test Method for Pitting or Crevice Corrosion of Metallic Surgical Implant
F746 Materials
ASTM Standard Test Method for Measuring Fretting Corrosion of Osteosynthesis Plates
F897 and Screws
ASTM
Standard Test Method for Corrosion of Surgical Instruments
F1089
ASTM
Standard Practice for Corrosion Fatigue Testing of Metallic Implant Materials
F1801
ASTM Standard Test Method for Conducting Cyclic Potentiodynamic Polarization
F2129 Measurements to Determine the Corrosion Susceptibility of Small Implant Devices
ASTM Standard Reference Test Method for Making Potentiodynamic Anodic Polarization
G5 Measurements
ASTM
Standard Guide for Laboratory Immersion Corrosion Testing of Metals
G31
ASTM Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless
G48 Steels and Related Alloys by Use of Ferric Chloride Solution
Standard Test Method for Conducting Cyclic Potentiodynamic Polarization
ASTM
Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-
G61
Based Alloys
ASTM Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in
G71 Electrolytes

2. CORROSION OF VARIOUS BIOMETALS


2.1 Stainless Steel

Stainless steel especially 316L is extensively utilized at many biomedical implementations because of its easy availability,
better corrosion defiance, fabrication properties and its lower cost. The main alloying elements in surgical grade SS 316L
are Cr (17-20%), Mo (2-3%),Ni (12-15%), and small number of some other elements. If it corrodes in the body, then

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26 Mileend P. Sharma

release of these ions are found to be powerful carcinogens and allergens. Stainless Steel is most susceptible towards pitting
and crevice corrosion, studies shows that pitting and crevice make up 90% of all failures of implants. SS is vulnerable to
localized corrosion by halogens (especially Cl -) and reduced sulphur compounds. In body, the company of living
microorganism often lead to localized damage. In SS, the main element responsible for high passivation layeris Chromium,
more amount of Chromium with some increase in Molybdenum provides increase in resistance to local passive layer
breakdown. If high amount of carbon is present it will increase chance of intergranular corrosion. So usually in biomedical
purpose SS have low content of carbon. The Nickel present in SS may produce some harmful effect due to nickel ions
released which are toxic for the body. This problem can be solved by adding Nitrogen in SS which increases resistance to
local attacks and passive film stability. But very high amount of nitrogen may also create problems like cause brittleness,
makes precipitates of nitride. Usually nitrogen is kept under 0.9% of total mass for medical applications.[1, 10]

2.1 Titanium and its Alloys

Titanium along with its mixtures likeTi-6Al-7Nb, Ti-6Al-4V,TiNi are frequently used in making biomaterials due to high
corrosion resistance, lower elastic modulus, greater specific strength and biocompatibility. Titanium has two different
phases (α and β) so by adding different stabilizers any or both phases can be found in the implant. Titanium has very high
pitting potentials, it means pitting corrosion in Ti and its alloys take place at very high anodic potential so it is not relevant
to biomedical applications. The maximum corrosion defiance in titanium was because of instant acquiescent layer for
mationon the surface. The passive film mainly consist of TiO2. High corrosion defiance of Ti is because of
thermodynamically stable oxide TiO2. A thin layer of oxide film may be enough to stop corrosion, more than thickness the
crystalline structure of passive film plays more important role. If the film is crystalline defects may easily pass through
them and the film would break down but if the oxide layer is amorphous then the defects will not be able to easily move,
and corrosion resistance will increase. The wear defiance of titanium along with its mixtures was comparatively less so
their use is unwise in implants where wear should be taken in consideration. Due to wear of titanium and release of wear
debris in tissue, Metallosis is often seen as a result. Titanium and its alloys are usually found in implants used for joint
replacement, dental implants, bone fixation, artificial heart valves and stents, pacemakers.[7, 8]

Cobalt-Based Alloys

Cobalt rooted mixtures contain maximum corrosion defiance, including crevice corrosion. It is also resistant to fatigue and
environment-induced cracking. In early 90’s Co-Cr alloys were used as alternatives of gold in dentistry. Chromium is an
important alloy in Co based alloys as it enhances solid compound reinforcement along with corrosion defiance of the
blend. Co-Cr alloys have better wear resistance than titanium and its alloys and stainless steel. The low ductility in Co-Cr
alloys is their main disadvantage. Co-Cr-Mo blends are consumed in stem as well as head of artificial joints, Cr-Co-W-Ni
alloy are used in bone fixation wires. In dentistry, Cr-Co-Mn, Co-Cr-Ni, Co-Cr-Ni-Cu blends were applied for orthodontic
wire and denture roots. For cardiovascular field Co-Cr-Fe-Ni, Co-Ni-Cr-Mo and Cr-Co-Ni-W-Fe alloys were utilized for
stents while Cr-Co blends are used for guide wires.[1, 4]

2.2 Biodegradable Metals

Corrosion of metal is seen as negative as it leads to failure, but in case of biodegradable material corrosion helps. Iron
based alloys and Magnesium alloys are the two main biodegradable materials. Biodegradable metals mean that they can
reduce in the body environment without any harmful effect after completing their work as the implants. Iron rooted

Impact Factor (JCC): 5.5893 NAAS Rating: 2.79


Corrosion of Bio-Materials 27

inculcates contains pure Iron (Fe) and Iron Manganese (Fe-Mn) mixtures. Iron can produce Fe+2 or Fe+3 ions through either
receiving or donating electrons that was beneficial for myoglobin, haemoglobin as well as major enzymes. Irons also have
high mechanical effects, high Young’s modulus and high radial strength. Magnesium alloys are also widely used in
biodegradable alloys. Biodegradable metals have less thrombogenicity as well as were also biocompatible. Mg is essential
constituent of tissue, non-carcinogenic and crucial to living organism. Biodegradable metallic stents used in coronary
stents are one of the core applications areas of biodegradable metals. The main benefits of biodegradable implants is there
was no requirement for second surgery to eliminate the implants[5, 8].

CONCLUSIONS

In this paper summary of corrosion of different bio metallic substances at body environment (in-vivo) is covered. The most
used metals for biomedical applications are Stainless steel 316L, Co-Cr mixtures as well asTitanium and its mixtures.
Corrosion defiance of the metal is a significant factor in selection of metal and design for implants. Even though surface
modification is not discussed much in this paper, it enhances the corrosion defiance of the metal. Titanium as well as its
mixtures offer best corrosion resistance, second to them are Co based alloys and then Stainless steel 316L. Galvanic,
pitting, crevice, fretting and corrosion fatigue are some of the most common types of corrosion seen in in-vivo
environment. In the in-vivo environment, the formation of stable passive layers plays a very important role. The passive
layer is one of the main protection of metals against corrosion. In the human body, different parts have different condition
so selection and design of metals should consider that. Failure of bio metallic components may cause toxic reactions in the
body. So, the corrosion of such implants have very less margin of error than when used in other fields. Even though much
testing and research is conducted the field of corrosion in biological system is still new and much more is to come in the
future.

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