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Corrosion and its control
Corrosion and its control
• Definition: The process of decay of metal by environmental
attack is called corrosion.
• Pure metals are extracted from their ores. Metals are used
to manufacturing different articles.
• These articles undergo corrosion, when they are exposed to
environment.
Disadvantages with corrosion:
1. Loss of useful metallic properties such as
Malleability, Ductility, Tensile strength and
Conductance.
2. Lifespan of machineries reduced.
3. Failure of machinery working.
4. Economic loss: it is estimated that the amount of
iron wasted by corrosion each year about 25% of its
annual world production.
2016 Kanpur train-accident: Not
conspiracy, corrosion blamed for 152
deaths
Using TRIZ to Develop New Corrosion
Protection Concepts in Shipbuilding
CBS Gouliguda-Hyderabad
Types of corrosion /Theories of corrosion
• Corrosion is two types :
1. Dry corrosion (or) Chemical corrosion.
2. Wet corrosion (or) Electrochemical corrosion.
1.chemical corrosion : The direct chemical reaction
of environmental gases such as O2, Cl2, HCl,..etc. on
metal, in the absence of moisture is called dry
corrosion or chemical corrosion.
• Types chemical corrosion:
• 1. Corrosion due to oxygen.
• 2. Corrosion due to other gases.
• 3. Liquid metal corrosion.
Oxidation corrosion
• All the metals have low electronegativity, so metals
readily undergo oxidation and form metal ions and
electrons, atmospheric oxygen absorb these
electrons & converted to oxide ions at low and high
temperature.
• Metal ions and oxide ion combine to form metal
oxides.
• These metal oxides form a uniform layer on the
metal surface.
• Further oxidation depends on nature of metal oxide
formed.
• 1. If the metal oxide layer is unstable: Reverse
reaction takes place, Corrosion does not takes place.
• 2.If the metal layer is stable, sticky and fine grain
structure. It prevent the further oxidation or corrosion.
• Examples: Aluminium(Al), Tin(Sn), Lead(Pb),
Copper(Cu), Chromium(Cr), Tungsten(W).
• 3. If metal oxide layer is volatile: Metal oxide formed
and removed from the metal surface to from fresh
metal surface for further oxidation.
• Example: Molybdenum oxide(MoO3).
. 4.If the metal oxide layer having pores and cracks:
Through which atmospheric oxygen penetrate into
metal surface, further oxidation continues.
Example: Lithium(Li), Potassium(K), Sodium(Na),
Magnesium(Mg).
• Pilling Bedworth Rule: it says that “smaller the specific
volume ratio greater is the oxidation corrosion”
• i. If VMO > VM, metal oxide layer is tight and non porous
and protect to further oxidation.
• Example: Tungsten(W)- 3.6, Chromium(Cr)- 2.0,
Nickel(Ni)-1.6. So rate of corrosion: Ni > Cr > W.
• ii. If VMO < VM, metal oxide layer is porous and non
protective, corrosion continues till all the metal
undergo oxidation corrosion.
• Example: Lithium(Li), Sodium(Na), Potassium(K).
2. Corrosion by other gases: Chlorine(Cl2), Carbon
dioxide(CO2), Sulphur dioxide(SO2) and hydrogen
sulphide(H2S).
• 2Ag + Cl2 ---- 2AgCl (Stable, Protective)
• Sn + 2Cl2 ---- SnCl4 (Volatile, Non protective)
• it is depends on the nature of metal and metal
oxide formed. Same pilling bedworth rules applied.
3. Liquid metal corrosion: when metal exposure to
liquid metals, react with the liquid metal and
undergo corrosion to form solution.
• Zn + 2HCl ----- ZnCl2 + H2
• Zn + Hg ------ Zn-Hg
2. Wet corrosion / Electro chemical corrosion
• Takes place in presence of moisture.
• More effective than dry corrosion.
• Takes place in acidic and neutral medium.
• Cathodic and anodic areas are formed on same
metal surface , separated by conducting medium.
• Types of wet corrosion:
• i. Evolution of Hydrogen gas type.
• Ii. Absorption of Oxygen gas type.
i. Evolution of Hydrogen gas type
• This type of corrosion takes place, when anodic
area is large and cathodic area is small.
ii. Absorption of Oxygen gas type
• This type of corrosion takes place, when anodic
area is small and cathodic area is large.
• This type of corrosion takes place, when metal have
cracks, rough surfaces, joints, bends…….etc.
• Absorption of oxygen gas takes place at cathodic
area and corrosion takes place at anodic area.
• Rust formed at the junction of cathod and anode.
Difference between dry & wet corrosion
Types of electrochemical corrosion:
• Galvanic corrosion:
• It is also known as bimetallic corrosion.
• It is an electrochemical process whereby one metal
corrodes in preference to another metal that it is in
contact with through an electrolyte.
• Galvanic corrosion occurs when two dissimilar
metals are immersed in a conductive solution and
are electrically connected.
Galvanic Series: When all the metals and their alloys are
arranged according to their increasing order of nobility.
Top metal and their alloys are more susceptible to
corrosion due less reduction potential values.
The bottom elements are more inert to corrosion due to
nobility of metals.
• Waterline Corrosion: When water is stored in a
metallic tank, it is observed that the metal below
the waterline gets corroded.
• It is because the water below the waterline is
poorly oxygenated and acts as an anode.
• The metal above the waterline is highly oxygenated
and acts as a cathode.
• Pitting corrosion:
• It is a localized form of corrosion by which cavities
or "holes" are produced in the material.
• Pitting is considered to be more dangerous than
uniform corrosion damage because it is more
difficult to detect, predict and design against.
• Corrosion products often cover the pits.
Factors effecting the corrosion
1. Position in Galvanic Series
• Metal which has lower reduction potential,
greater is the tendency of corrosion.
• Rate of corrosion α
1
Reduction potential
• If two metals were joined difference in reduction
potential increases, rate of corrosion increases.
2. Overvoltage
• Rate of corrosion α
1
Overvoltage
• Zn + HCl -------------- ZnCl2 + H2 EMF =0.76V
• Hydogen overvoltage is 0.76V
• Zn + CuSO4 -------------- ZnSO4 + Cu EMF= 1.1V
• Hydogen overvoltage is 1.1 - 0.76 = 0.34V
3. Relative Area of Cathodic and
Anodic Surfaces
• Cathodic Area > Anodic Area, Then
_____________ corrosion takes place
• Anodic Area > Cathodic Area, Then
_____________ corrosion takes place
4. Purity of Metal
Percentage of
Aluminium(Al) 99.998 99.97 99.2
Rate of Reaction
with HCl 1 1000 30,000
Rate of corrosion α
1
Purity of metals
Purity of metal decreases i.e. foreign metal content
increases , electrochemical corrosion accelerated. So that
metals easily undergo corrosion.
5. Nature of surface films
• Porous---
• Non porous…
• Unstable..
• 6. Solubility of corrosion products
• 7. Volatility of corrosion products
Nature of Environment
• Temperature
• pH
• Humidity
• Nature of ions present
• Conductance of corroding Medium
• Impurities
Corrosion control methods
• Cathodic protection: The method of protection
given to a metal by forcefully making it to behave
like a cathode is called cathodic protection.
• This is done by two ways :
• 1. Sacrificial anodic protection.
• 2. Impressed current cathodic method.
Sacrificial anodic protection
• In this method the metallic structure used to be
protected is called base metal.
• The base metal is connected to more anodic metal
through a wire.
• The anode metal undergoes corrosion slowly,
while the base metal is protected.
• The corroded sacrificial anode block is replaced by
a fresh one.
• The commonly used anodic metals are Aluminium,
Zinc, Magnesium and their Alloys.
Applications
Impressed current cathodic method
• In this method an impressive current little more
than corrosion current is applied in the opposite
direction to nullify the corrosion current producing
a reverse cell reaction.
• Thus, the anodic corroding metal become cathodic
and protected from corrosion.
• The impressed current taken from a battery or
alternative current(A.C.) line.
• The anode is usually insoluble anode like graphite,
high silica iron, scrap iron, stainless steel, platinum.
• Applications:
• This method is applicable to large structures, for
long term use.
• Water tanks,
• buried water or oil pipelines,
• Marine pipes,
• Transmission line towers.
Surface coating or protective coatings
• This is the oldest method of protection of metals.
• The coated surface isolated from the metal from its
corroding environment or surroundings.
• https://www.youtube.com/watch?v=Qi-tK1jwO-k
• Requirements for surface coating:
• Coating compound must be chemically inert.
• Resistant to environmental conditions such as
temperature, pressure, humidity…….etc.
• Coating must be prevent the passage of
environmental gases onto the metal suface.
Methods of cleaning of surface of metal
• Solvent cleaning:
• Before applying any protective coating the metal
surface must be thoroughly cleaned to remove
dirt, old protective coatings such as oils,
greases…..etc.
• Cleaning of metal surface by the application of
organic solvents like Naphthalene, chlorinated
hydrocarbons, toluene, xylene or Acetone.
• Then the metal surface is cleaned with steam and
hot water containing reagents like alkali.
• Alkaline cleaning: Metal surface cleaned with alkali
agents like sodium phosphate(Na3PO4) along with
soaps and caustic soda(NaOH).
• This method removes old paint coatings from metal
surface.
• Alkali treatment followed by cleaning with 0.1%
chromic acid to remove traces of alkali.
• Mechanical cleaning: This method used to to
remove loose rust, scales, dirt ..etc. from the metal
surface.
• This is done by using metal brushes, sand papers,
detergents followed by steam or hot water
treatment.
• https://www.youtube.com/watch?v=uCZxr9IzRi0
• Flame cleaning: In this method material is
heated followed by vibration wire brushing.
• https://www.youtube.com/watch?v=ACGSzBXKONo
• Sandblasting:
https://www.youtube.com/watch?v=AKrg2cRNxkM
• This method used to remove scales, rust from metal
surface and make it smooth and ready to coating.
• Pickling and etching:
• In this process metals are immersed in acid solutions.
• Generally dilute H2SO4 or dilute HCl or dilute HNO3 and
their mixtures are used.
• This method provides clean and smooth surface for
applying protective coating.
Metallic coatings
• In this method, coating of a metal on the surface of
other metal
• The metal which is protected is called base metal,
and the metal which is coated on the surface of
the base metal is called coating metal.
• Metallic coatings are two types:
• Anodic coatings:
• Coating of inferior metal on base metal.
Example: Galvanization
• Cathodic coating:
• Coating of superior metal on base metal.
Example: Tinning
Methods of application
• Hot dipping.
Ex. i. Galvanization, Tinning.
• Metal cladding.
Ex. Metal sandwiching.
• Electroplating and
• Electroless plating.
Galvanization
Electroless plating / chemical plating
/autocatalytic plating
• The deposition of a metal from its salt solution on a
catalytically active surface by a suitable reducing
agent, without using electrical energy is called
electroless plating.
The following are the requirements for electroless
plating
• Soluble electroactive metal in the form of metal
chloride or metal sulphate.
• The reducing agents like formaldehyde,
hypophosphite.
• Complexating agents like citrate, tartate and
succinate.
• Exaltants like succinate, glycinates and fluorides to
improve the rate of plating.
• Stabilizers which prevent decomposition of bath.
• To control pH of the bath buffer solution was
added.
Electroless plating of nickel
• Base material: Acrylonitrile-Butadiene-Styrene(ABS)
polymer.
• Coating metal : Nickel (Ni)
• The base material is activated by SnCl2 (stannous
chloride) followed by PdCl2 (palladium chloride )to
get a layer of palladium(Pd) and the surface is dried.
• The base metal dipped in a solution of nickel
chloride(NiCl2), sodium dihydrogen phosphite
(NaH2PO2), Buffer solution(CH3COOH + CH3COONa)
and Sodium succinate as complexating agent and
exalt, pH of bath maintained at 4.5 and
temperature at 930 C.
•
Applications
• Electroless plated nickel objects are better corrosion
resistance , pore free, hard and wear assistant.
• Used in electronic applications providing a non
magnetic underlay in magnetic components.
• ABS plastics are used for decorative applications
such as car finishing's, perfume bottle caps,
costume jewellery and Hi-Fi equipments.

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Corrosion and its control

  • 2. Corrosion and its control • Definition: The process of decay of metal by environmental attack is called corrosion. • Pure metals are extracted from their ores. Metals are used to manufacturing different articles. • These articles undergo corrosion, when they are exposed to environment.
  • 3. Disadvantages with corrosion: 1. Loss of useful metallic properties such as Malleability, Ductility, Tensile strength and Conductance. 2. Lifespan of machineries reduced. 3. Failure of machinery working. 4. Economic loss: it is estimated that the amount of iron wasted by corrosion each year about 25% of its annual world production.
  • 4. 2016 Kanpur train-accident: Not conspiracy, corrosion blamed for 152 deaths
  • 5. Using TRIZ to Develop New Corrosion Protection Concepts in Shipbuilding
  • 6.
  • 8. Types of corrosion /Theories of corrosion • Corrosion is two types : 1. Dry corrosion (or) Chemical corrosion. 2. Wet corrosion (or) Electrochemical corrosion. 1.chemical corrosion : The direct chemical reaction of environmental gases such as O2, Cl2, HCl,..etc. on metal, in the absence of moisture is called dry corrosion or chemical corrosion. • Types chemical corrosion: • 1. Corrosion due to oxygen. • 2. Corrosion due to other gases. • 3. Liquid metal corrosion.
  • 9. Oxidation corrosion • All the metals have low electronegativity, so metals readily undergo oxidation and form metal ions and electrons, atmospheric oxygen absorb these electrons & converted to oxide ions at low and high temperature. • Metal ions and oxide ion combine to form metal oxides. • These metal oxides form a uniform layer on the metal surface. • Further oxidation depends on nature of metal oxide formed. • 1. If the metal oxide layer is unstable: Reverse reaction takes place, Corrosion does not takes place.
  • 10. • 2.If the metal layer is stable, sticky and fine grain structure. It prevent the further oxidation or corrosion. • Examples: Aluminium(Al), Tin(Sn), Lead(Pb), Copper(Cu), Chromium(Cr), Tungsten(W). • 3. If metal oxide layer is volatile: Metal oxide formed and removed from the metal surface to from fresh metal surface for further oxidation. • Example: Molybdenum oxide(MoO3). . 4.If the metal oxide layer having pores and cracks: Through which atmospheric oxygen penetrate into metal surface, further oxidation continues. Example: Lithium(Li), Potassium(K), Sodium(Na), Magnesium(Mg).
  • 11. • Pilling Bedworth Rule: it says that “smaller the specific volume ratio greater is the oxidation corrosion” • i. If VMO > VM, metal oxide layer is tight and non porous and protect to further oxidation. • Example: Tungsten(W)- 3.6, Chromium(Cr)- 2.0, Nickel(Ni)-1.6. So rate of corrosion: Ni > Cr > W. • ii. If VMO < VM, metal oxide layer is porous and non protective, corrosion continues till all the metal undergo oxidation corrosion. • Example: Lithium(Li), Sodium(Na), Potassium(K).
  • 12. 2. Corrosion by other gases: Chlorine(Cl2), Carbon dioxide(CO2), Sulphur dioxide(SO2) and hydrogen sulphide(H2S). • 2Ag + Cl2 ---- 2AgCl (Stable, Protective) • Sn + 2Cl2 ---- SnCl4 (Volatile, Non protective) • it is depends on the nature of metal and metal oxide formed. Same pilling bedworth rules applied. 3. Liquid metal corrosion: when metal exposure to liquid metals, react with the liquid metal and undergo corrosion to form solution. • Zn + 2HCl ----- ZnCl2 + H2 • Zn + Hg ------ Zn-Hg
  • 13. 2. Wet corrosion / Electro chemical corrosion • Takes place in presence of moisture. • More effective than dry corrosion. • Takes place in acidic and neutral medium. • Cathodic and anodic areas are formed on same metal surface , separated by conducting medium. • Types of wet corrosion: • i. Evolution of Hydrogen gas type. • Ii. Absorption of Oxygen gas type.
  • 14. i. Evolution of Hydrogen gas type • This type of corrosion takes place, when anodic area is large and cathodic area is small.
  • 15. ii. Absorption of Oxygen gas type • This type of corrosion takes place, when anodic area is small and cathodic area is large. • This type of corrosion takes place, when metal have cracks, rough surfaces, joints, bends…….etc. • Absorption of oxygen gas takes place at cathodic area and corrosion takes place at anodic area. • Rust formed at the junction of cathod and anode.
  • 16.
  • 17. Difference between dry & wet corrosion
  • 18. Types of electrochemical corrosion: • Galvanic corrosion: • It is also known as bimetallic corrosion. • It is an electrochemical process whereby one metal corrodes in preference to another metal that it is in contact with through an electrolyte. • Galvanic corrosion occurs when two dissimilar metals are immersed in a conductive solution and are electrically connected.
  • 19. Galvanic Series: When all the metals and their alloys are arranged according to their increasing order of nobility. Top metal and their alloys are more susceptible to corrosion due less reduction potential values. The bottom elements are more inert to corrosion due to nobility of metals.
  • 20.
  • 21. • Waterline Corrosion: When water is stored in a metallic tank, it is observed that the metal below the waterline gets corroded. • It is because the water below the waterline is poorly oxygenated and acts as an anode. • The metal above the waterline is highly oxygenated and acts as a cathode.
  • 22. • Pitting corrosion: • It is a localized form of corrosion by which cavities or "holes" are produced in the material. • Pitting is considered to be more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against. • Corrosion products often cover the pits.
  • 24. 1. Position in Galvanic Series • Metal which has lower reduction potential, greater is the tendency of corrosion. • Rate of corrosion α 1 Reduction potential • If two metals were joined difference in reduction potential increases, rate of corrosion increases.
  • 25. 2. Overvoltage • Rate of corrosion α 1 Overvoltage • Zn + HCl -------------- ZnCl2 + H2 EMF =0.76V • Hydogen overvoltage is 0.76V • Zn + CuSO4 -------------- ZnSO4 + Cu EMF= 1.1V • Hydogen overvoltage is 1.1 - 0.76 = 0.34V
  • 26. 3. Relative Area of Cathodic and Anodic Surfaces • Cathodic Area > Anodic Area, Then _____________ corrosion takes place • Anodic Area > Cathodic Area, Then _____________ corrosion takes place
  • 27. 4. Purity of Metal Percentage of Aluminium(Al) 99.998 99.97 99.2 Rate of Reaction with HCl 1 1000 30,000 Rate of corrosion α 1 Purity of metals Purity of metal decreases i.e. foreign metal content increases , electrochemical corrosion accelerated. So that metals easily undergo corrosion.
  • 28. 5. Nature of surface films • Porous--- • Non porous… • Unstable.. • 6. Solubility of corrosion products • 7. Volatility of corrosion products
  • 29.
  • 30. Nature of Environment • Temperature • pH • Humidity • Nature of ions present • Conductance of corroding Medium • Impurities
  • 31. Corrosion control methods • Cathodic protection: The method of protection given to a metal by forcefully making it to behave like a cathode is called cathodic protection. • This is done by two ways : • 1. Sacrificial anodic protection. • 2. Impressed current cathodic method.
  • 32. Sacrificial anodic protection • In this method the metallic structure used to be protected is called base metal. • The base metal is connected to more anodic metal through a wire. • The anode metal undergoes corrosion slowly, while the base metal is protected. • The corroded sacrificial anode block is replaced by a fresh one. • The commonly used anodic metals are Aluminium, Zinc, Magnesium and their Alloys.
  • 34.
  • 35. Impressed current cathodic method • In this method an impressive current little more than corrosion current is applied in the opposite direction to nullify the corrosion current producing a reverse cell reaction. • Thus, the anodic corroding metal become cathodic and protected from corrosion. • The impressed current taken from a battery or alternative current(A.C.) line. • The anode is usually insoluble anode like graphite, high silica iron, scrap iron, stainless steel, platinum.
  • 36. • Applications: • This method is applicable to large structures, for long term use. • Water tanks, • buried water or oil pipelines, • Marine pipes, • Transmission line towers.
  • 37.
  • 38.
  • 39. Surface coating or protective coatings • This is the oldest method of protection of metals. • The coated surface isolated from the metal from its corroding environment or surroundings. • https://www.youtube.com/watch?v=Qi-tK1jwO-k • Requirements for surface coating: • Coating compound must be chemically inert. • Resistant to environmental conditions such as temperature, pressure, humidity…….etc. • Coating must be prevent the passage of environmental gases onto the metal suface.
  • 40. Methods of cleaning of surface of metal • Solvent cleaning: • Before applying any protective coating the metal surface must be thoroughly cleaned to remove dirt, old protective coatings such as oils, greases…..etc. • Cleaning of metal surface by the application of organic solvents like Naphthalene, chlorinated hydrocarbons, toluene, xylene or Acetone. • Then the metal surface is cleaned with steam and hot water containing reagents like alkali.
  • 41. • Alkaline cleaning: Metal surface cleaned with alkali agents like sodium phosphate(Na3PO4) along with soaps and caustic soda(NaOH). • This method removes old paint coatings from metal surface. • Alkali treatment followed by cleaning with 0.1% chromic acid to remove traces of alkali. • Mechanical cleaning: This method used to to remove loose rust, scales, dirt ..etc. from the metal surface. • This is done by using metal brushes, sand papers, detergents followed by steam or hot water treatment. • https://www.youtube.com/watch?v=uCZxr9IzRi0
  • 42. • Flame cleaning: In this method material is heated followed by vibration wire brushing. • https://www.youtube.com/watch?v=ACGSzBXKONo • Sandblasting: https://www.youtube.com/watch?v=AKrg2cRNxkM • This method used to remove scales, rust from metal surface and make it smooth and ready to coating. • Pickling and etching: • In this process metals are immersed in acid solutions. • Generally dilute H2SO4 or dilute HCl or dilute HNO3 and their mixtures are used. • This method provides clean and smooth surface for applying protective coating.
  • 43. Metallic coatings • In this method, coating of a metal on the surface of other metal • The metal which is protected is called base metal, and the metal which is coated on the surface of the base metal is called coating metal. • Metallic coatings are two types: • Anodic coatings: • Coating of inferior metal on base metal. Example: Galvanization • Cathodic coating: • Coating of superior metal on base metal. Example: Tinning
  • 44. Methods of application • Hot dipping. Ex. i. Galvanization, Tinning. • Metal cladding. Ex. Metal sandwiching. • Electroplating and • Electroless plating.
  • 46.
  • 47.
  • 48.
  • 49. Electroless plating / chemical plating /autocatalytic plating • The deposition of a metal from its salt solution on a catalytically active surface by a suitable reducing agent, without using electrical energy is called electroless plating.
  • 50. The following are the requirements for electroless plating • Soluble electroactive metal in the form of metal chloride or metal sulphate. • The reducing agents like formaldehyde, hypophosphite. • Complexating agents like citrate, tartate and succinate. • Exaltants like succinate, glycinates and fluorides to improve the rate of plating. • Stabilizers which prevent decomposition of bath. • To control pH of the bath buffer solution was added.
  • 51. Electroless plating of nickel • Base material: Acrylonitrile-Butadiene-Styrene(ABS) polymer. • Coating metal : Nickel (Ni) • The base material is activated by SnCl2 (stannous chloride) followed by PdCl2 (palladium chloride )to get a layer of palladium(Pd) and the surface is dried. • The base metal dipped in a solution of nickel chloride(NiCl2), sodium dihydrogen phosphite (NaH2PO2), Buffer solution(CH3COOH + CH3COONa) and Sodium succinate as complexating agent and exalt, pH of bath maintained at 4.5 and temperature at 930 C.
  • 52.
  • 53. Applications • Electroless plated nickel objects are better corrosion resistance , pore free, hard and wear assistant. • Used in electronic applications providing a non magnetic underlay in magnetic components. • ABS plastics are used for decorative applications such as car finishing's, perfume bottle caps, costume jewellery and Hi-Fi equipments.