Sei sulla pagina 1di 6

Lecture 29: MIC and Biofilms

NPTEL Web Course

Lecture 29
MIC and Biofilms
Keywords: Biofilms, Potential Ennoblement, Indirect Role.

Microbially-influenced corrosion (MIC) in natural marine environments involves


two biomediated consequences:
a) Corrosion potential ennoblement.
b) Sulfate reduction-biogenic sulfide formation.

High stainless alloys (Ni-Cr-Mo), titanium alloys, platinum and gold (noble
metals) are capable of sustaining ennobled corrosion potential without enhanced
susceptibility to crevice corrosion.
Common stainless steels also exhibit corrosion potential ennoblement But
highly amenable to localised crevice corrosion.
Irrespective of cuprous ion toxicity, copper alloys are not immune to biofouling.
Microorganisms having high copper tolerance can attach and colonise on copper
base alloys. Some copper alloys exhibit potential ennoblement. Invariably, MIC
of copper alloys is caused by biogenic sulfides due to presence of SRB.

For selection of alloys for marine applications, susceptibility for crevice corrosion is
often the limiting factor. For most of the passive alloys, formation of biofilms
results in corrosion potential ennoblement, in sea water and brackish waters.
Microbially-deposited manganic and ferric oxides could well be the reason behind
such ennoblement followed by localised corrosion.

Proposed mechanisms for ennoblement in marine environments can be based on


three aspects, namely, thermodynamic, kinetic and changes in the nature of the
1
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 29: MIC and Biofilms

NPTEL Web Course

reduction reaction. pH changes in the metal-film interface or an increase in partial


pressure of oxygen can influence the potential of the oxygen reaction leading to
ennoblement in corrosion potential. Shifts in the exchange current density for the
oxygen reduction also would result in shift in the potential. Pitting potentials would
also be affected under the conditions of ennoblement. Kinetic interpretation of
ennoblement implies changes in oxygen reduction kinetics due to increase in
exchange current densities. Cathodic oxygen reduction rates could be enhanced due
to increase in exchange currents and biopolymers in the biofilm could further
catalyze the cathodic reaction. Bio-enzymes are known to be excellent catalysts for
several electrochemical reactions.

Another viewpoint is the role of bacterial siderophores that possess excellent


corrosion inhibition properties. The model for predicting SRB-mediated corrosion is
based on the possibility of the metal interacting with biogenic sulfides. Reducing
environment generated by bacterial sulfate reduction in the biofilms can destabilize
the surface oxide (passive) layer, leading to metal dissolution. Thermodynamic
feasibility for the conversion of metal oxide to sulfide need be ascertained.

Corrosion and Ennoblement through biogenic manganese and iron oxide


deposition
Microbial colonization of metals and alloys can influence the mechanisms and rate
of electrochemical reactions. For example, ennoblement of passive metals such as
stainless steels and titanium can occur due to positive shifts in their open circuit
potentials in the presence of microbial colonies. An increase in cathodic current
density during cathodic polarization is often associated with enhancement of open
circuit potentials.

Biofilm formation on stainless steels changed their

electrochemical behavior through significant positive shifts in open circuit potentials


and increase in cathodic currents. Similar behavior could be observed on titanium as

2
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 29: MIC and Biofilms

well.

NPTEL Web Course

Microbial colonization responsible for such ennoblement results in

biogeneration of extracellular substances, organo metallic complexes and metal


specific enzymes. Microbially-modified acidification at metal-solution interfaces
and generation of oxidants such as H2O2 can also cause ennoblement. Microbial
production of passivating siderophores is yet another possibility.

Microbial

deposition of iron and manganese oxides / hydroxides can lead to ennoblement of


passive metals. Iron and manganese oxidizing bacteria inhabiting fresh and sea
waters as well as soils can attach and colonise on metal surfaces and precipitate
manganic and iron oxyhydroxides.
Mn+2 + 2H2O = MnO2 + 4H+ + 2e
MnOOH + OH- = MnO2 + H2O + e
Depending on the pH of water, the above reactions can influence the measured open
circuit potentials to deviate in a nobler direction.

Electrochemical oxidation/reduction of manganese and iron is part of the natural


manganese and iron cycles in natural environments.

Both manganese and iron

oxidizing and reducing microorganisms take part in the cycle involving biochemical
and electrochemical pathways.

Microbially produced MnO2 can also corrode active metals such as mild steel
Fe + MnO2 + 4H+ = Fe++ + Mn++ + 2H2O
Manganese oxidizing organisms can corrode stainless steel welds.
Mn-oxidizing microbes have been implicated in the microbial corrosion of stainless
steel welds. Formation of MnO2 ennobles its potential in natural environments. Due
to ennoblement, potentials shift above repassivation potential to the pitting potential.

Mn++ + O2

MnO2
3

Course Title: Advances in Corrosion Engineering


Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 29: MIC and Biofilms

NPTEL Web Course

Indirect role of Microorganisms in MIC


Role of SRB in cathodic depolarization through consumption of hydrogen iron has
been discussed as a direct attack mechanism.
Bacterial and fungal metabolites such as organic acids may decrease anodic
polarization. Many biogenic organic acids such as citric and oxalic acids can form
soluble metal ion complexes, promoting anodic oxidation. Similarly mineral acids
such as sulfuric acid and nitric acids can be produced by microbes promoting metal
dissolution. Microbially-generated phosphorus compounds and H2O2 produced in
biofilms are aggressive corrosive agents.
In many industrial water systems bacterial colonization of metal surfaces lead to
slime formation containing extracellular polysaccharides. Slime-coated organisms
provide conducive environment of further microbial growth. A slime (or capsuble)
surrounding attached bacterium protects them from biocides and corrosion inhibitors.
Developments of concentration cells under the biofilms (oxygen and ion
concentration gradients) trigger formation of anodic and cathodic areas, promoting
corrosion.

Identification and enumeration of slime-forming microorganisms are

important tools to predict MIC in cooling water systems. Many iron and manganese
oxidizing bacteria contribute to formation of oxide scales on metal surfaces.
Presences of chloride ions aggravate corrosion since they destroy oxides and
passivity.
Disruption of passive films and oxide layers from metal surfaces through biofilm
formation and SRB metabolites has been discussed. Incorporation of extracellular
polymeric substances into the copper oxide film is suggested to be one of the reasons
for microbial corrosion of copper. 316 stainless steel interacted with and colonized
with of Citrobacter freundii was found to be subjected to local chromium depletion
under the passive layer. Similarly, depletion of iron with enrichment of sulfides
could be observed in steels subjected to SRB interaction. Many industrial failures
brought about by localised pitting in stainless steel condensers were identified as due

4
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 29: MIC and Biofilms

NPTEL Web Course

to MIC. Sulfoxy anions such as thiosulfates, and tetrathionates (SRB metabolites)


present in circulating water could reduce the pitting potential of stainless steels.
Continued activity of SRB would inhibit repassivation, when chloride ions are also
present.
Stress corrosion cracking of metals and alloys can be accelerated by microbial
processes. For example, Stresses can be induced by biologically generated sulfide
and hydrogen at neutral pH.

Similarly, corrosion fatigue can be biocatalyzed.

Microbial activity can influence cathodic hydrogen generation and its entry into the
metal matrix. Hydrogen embrittlement of steels can thus be contributed by microbial
activity. Further, biogenic sulfides such as H2S and thiosulfates can act as poisons
for the hydrogen recombination reaction and promote diffusion of atomic hydrogen
into steel matrix. Under cathodic protection conditions, especially in the presence of
SRB, hydrogen-induced stress cracking of steels could occur.
Other stress-inducing biogenic products include CO2. Biological degradation of
protective coatings can also occur.

Souring of petroleum products due to H2S

presence (due to SRB activity) is a serious problem.


Degradation of
Corrosion inhibitors
Coatings and paints
Lubricants and emulsions and
Cathodic protection systems.
are influenced by microbial activity. Microorganisms can grow in inhibitor-added
electrolytes utilizing the carbon and hydrogen present in the organic chemical.

5
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 29: MIC and Biofilms

NPTEL Web Course

Microorganisms are involved in corrosion in metal machining and processing


operation.
Destruction of
Anticorrosive agents in coolants.
Emulsions used in hydraulic fluids.
Oil emulsions at alkaline pH favours bacterial growth.

The microbes grow in

aqueous phase and metabolize on nutrients available (carbon,

nitrogen,

phosphorous). Due to microbial activity, degradation of emulsifiers takes place and


such an emulsion turns corrosive. Degradation of anticorrosive agents occurs in
coolants used in several engineering operations. Recirulated lubricants are prone to
bacterial infection.
Protective coatings are provided for buried structures and interior surfaces of tanks
and pipings. Microbial attacks can occur in chemical and polymer coatings.
Biodegradation of adhesives is yet another problem. Biodegradation of coatings on
pipe lines subjected to cathodic protection is of serious concern since it could
enhance current requirements for protection all of a sudden.

Experimental

observations have recorded increasing protection current requirements for pipe lines
under sub-soil conditions infested with SRB.
[Ref B.J. Little, J. S. Lee and R. I. Ray, The influence of marine biofilms on
corrosion, A concise Review, Electrochim. Acta; 54 (2008), 2-7].

6
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore