Вы находитесь на странице: 1из 41

Chapter 5

Corrosion Protection

Chapter 5 Corrosion Protection
Chapter 5 Corrosion Protection
Chapter 5 Corrosion Protection

Remember

The five essential components of the corrosion cell (or

Requirements for Electrochemical Corrosion )are:

1- Anodic Zones (A) 2- Cathodic Zones (C) 3- Electrical Contact Between Them

4- Ionically Conducting Solution

5- Cathodic Reactant (1+4 cathodic Reactions)

Electronic Path

i
i
Cathodic Reactant (1+4 cathodic Reactions) Electronic Path i ANODE (A) CATHODE (C) Where Corrosion Occurs!!!!
ANODE (A) CATHODE (C)
ANODE (A)
CATHODE (C)

Where Corrosion Occurs!!!!

Ionic-Current Path

Cathodic

Reaction

Metal or alloy

Anode + Cathode + Current Path

+

Corrosive Environment

Cathodic Reactant (1+4 !) + Ionic Current Path (moisture)

=

Cathodic Reactant (1+4 !) + Ionic Current Path (moisture) = Corrosion The Five Methods For Control

Corrosion

The Five Methods For Control Corrosion

Material Selection

Design

Changing the Environment

Changing the Metal Potential

Surface Coating (Zn, Sn, Plastic Paints etc)

1- Corrosion Control by Material selection

(selection of proper material for a particular

corrosive service depend on the environment)

a particular corrosive service depend on the environment)  Metallic [choose the proper metal or alloy]

Metallic [choose the proper metal or alloy]

Nonmetallic (use isolating joints and seals ) [rubbers (natural and synthetic), plastics, ceramics, carbon and

graphite, and wood]

Metals and Alloys

Metals and Alloys No Environment Proper material 1 Nitric acid Stainless steels 2 Caustic Nickel

No

Environment

Proper material

1

Nitric acid

Stainless steels

2

Caustic

Nickel and nickel alloys

3

Hydrofluoric acid

Monel (Ni-Cu)

4

Hot hydrochloric acid

Hastelloys (Ni-Cr-Mo) (Chlorimets)

5

Dilute sulfuric acid

Lead

6

Nonstaining atmospheric exposure

Aluminum

7

Distilled water

Tin

8

Hot strong oxidizing solution

Titanium

9

Ultimate resistance

Tantalum

10

Concentrated sulfuric acid

Steel

2- Control Corrosion by Design Modifications Corrosion Control must be properly addressed during the design,

2- Control Corrosion by Design Modifications

Corrosion Control must be properly addressed

during the design, installation, and subsequent operation of systems.

Design Do’s & Don’ts

To avoid SCC, you must avoid any excessive stresses.

To avoid galvanic corrosion, you must (1) avoid any contact between dissimilar

metals, (2) electrically isolate the two metals & (3) use high surface area anode.

To avoid erosion corrosion, you must avoid any sharp bends in piping systems especially when high velocities and/or solid in suspension are involved.

To avoid crevice/pitting corrosion, you must (1) avoid stagnant water/electrolyte (2) use good welding practice (weld rather than rivet) (3) use properly trimmed seals,

rubbers, and gaskets.

To avoid I.G.C, you must control the grain size and temperatures during the manufacturing steps.

Avoid sharp corners where paint tends to be thinner and often starts to fail.

Prevent solutions from drying/concentrating and ensure complete drainage of tanks

to avoid any differential aeration (conc.) corrosion.

Consider using paints & ceramics.

Consider cathodic protections (1) zinc plating (galvanization), (2) use of sacrificial anodes of Zn or Mg on steel ship hull (3) use of impressed voltage from a battery.

Design to exclude air except for active-passive metals and alloys, they require O 2 for protective films.

Most general rule : AVOID ANY HETEROGENEITY !!!

7

2014 - I

2014 - I 8
2014 - I 8
2014 - I 8
2014 - I 8
2014 - I 8
3- Corrosion Control by Changing the Environment • Removal of O 2 from the system

3- Corrosion Control by Changing the Environment

3- Corrosion Control by Changing the Environment • Removal of O 2 from the system Reactants

Removal of O 2 from the system

the Environment • Removal of O 2 from the system Reactants of the cathodic reaction accompanying

Reactants of the cathodic reaction accompanying the

corrosion process

Control of pH (H + ions)

Addition of complexing agents to remove (mask) the aggressive

ions

Addition of inhibitors to decrease the rate of oxidation and/or

reduction reactions

4- Control Corrosion by Changing the Metal Potential

4- Control Corrosion by Changing the Metal Potential Cathodic Protections Shifting the metal potential to a
4- Control Corrosion by Changing the Metal Potential Cathodic Protections Shifting the metal potential to a

Cathodic Protections

Shifting the metal potential to a more cathodic value. This shift in potential can be done by two different

methods.

(a)

Cathodic protection with impressed current

(b)

Cathodic protection with sacrificial

Anodic Protection

Shift metal potential into a

range

where passivation

occurs. This is done by applying an external DC current

to the anode (prior to its use) to

form a protective passive film.

anodes

Anodic Protection

If an active-passive alloy is

maintained in the passive region with a potentiostat, its corrosion rate will be reduced to i pass . This technique is based on the

formation of protective film on

metals by externally applied anodic currents.

film on metals by externally applied anodic currents. Anodic protection is based on passivation of the

Anodic protection is based on passivation of the metal surface by an application of an external DC current.

Cathodic Protection CP

Cathodic protection is achieved by supplying electrons to the

metal (anode) to be protected to force it to act as a cathode instead of acting as an anode. This applied negative current should be the positive corrosion current.

The CP is widely used in :

1) long pipe lines, 2) gas and oil transmission lines, 3) ships, 4) chemical processing equipment.

CP is widely used in : 1) long pipe lines, 2) gas and oil transmission lines,
Cathodic Protection Methods (a) Sacrificial Anode Method Current is supplied by connecting the object to

Cathodic Protection Methods

(a) Sacrificial Anode Method Current is supplied by connecting the object to a more reactive (easily corroded) metal as a sacrificial anode. i.e.

formation of galvanic cell in which the

sacrificial anode is consumed (sacrificed).

(b) Impressed Current Method Here, an external current is applied from a DC source (e.g. a battery) and auxiliary anode. i.e. an electrolytic cell

is formed where corrodible or inert

auxiliary anode can be used

cathode anode
cathode
anode
Cathodic Protection Methods (a) Sacrificial Anode Method Protection of Steel Structure By connecting a piece
Cathodic Protection Methods
(a) Sacrificial Anode Method
Protection of Steel Structure
By connecting a piece of Zinc, Al or other
anodic material to the steel, in this case,
the zinc or other anodic metal is termed
“Sacrificed Anode“.
Cathodic protection of a
ship hull using a zinc
sacrificial anode

Cathodic protection of an underground pipeline using a zinc sacrificial anode

Cathodic protection of an underground pipeline using a zinc sacrificial anode
Cathodic protection of an underground pipeline using a zinc sacrificial anode

Cathodic Protection Methods

(b) Impressed current Method

Cathodic Protection Methods (b) Impressed current Method
Cathodic Protection Methods (b) Impressed current Method
Stray current corrosion - Power + - + Power supply supply Ground Ground level level
Stray current corrosion
-
Power
+
-
+
Power
supply
supply
Ground
Ground
level
level
Steel
Current
Anode
Steel
Anode
Anode
tank
tank
Localized
corrosion
Steel pipe
Insulated
Steel pipe
connection
corrosion Steel pipe Insulated Steel pipe connection  It results from stray currents, i.e., current flowing

It results from stray currents, i.e., current flowing through passes other than

the intended circuit, e.g., from electrical railways, ground DC sources, etc. Stray current corrosion is basically independent of such environmental conditions as O 2 -concn or pH. Depending on the intensity of stray current (that is frequently higher than those produced by galvanic cells), corrosion may be very rapid.

In contrary to galvanic-type currents, stray currents operate over long

distances and seek for the least resistant path causing severe corrosion where it leaves the line. Knowing where stray currents are present is highly important when remedial measures are undertaken (Impressed Cathodic Protection) .

5- Corrosion Control by Surface Coatings

Normally, it is the first line of defense against corrosion: provides barrier between a corrosive environment and the structure.

No coating is perfect and usually contains of holidays (voids) often resulting from improper application and/or damage.

Coatings may act as sacrificial anode or release substance that inhibit corrosive

attack on substrate.

Coatings

that inhibit corrosive attack on substrate. Coatings Metallic coatings  Cathodic coatings Inert Barrier 
that inhibit corrosive attack on substrate. Coatings Metallic coatings  Cathodic coatings Inert Barrier 

Metallic coatings Cathodic coatings

Inert Barrier

Anodic coatings

Sacrificial Barrier

Non-metallic coatings

Inert Barrier

Sacrificial Barrier Non-metallic coatings Inert Barrier Application • Electroplating, • Chemical reduction

Application

Electroplating,

Chemical reduction (electroless plating),

Hot dipping (galvanization),

Metal Spraying, etc.

Inorganic coatings

Organic coatings (Painting)

Conversion coating

Portland cement coatings

Vitreous enamels

Metallic coatings: (a) Cathodic coatings (Inert Barrier) The coating metal is more noble than the
Metallic coatings: (a) Cathodic coatings (Inert Barrier)
The coating metal is more noble than the substrate metal.
i.e. the coating metal is cathodic with respect to the substrate.
e.g. the coating of iron with silver, copper, nickel, Co, Sn, Pb on steel.

This coating should be free of pores/discontinuity which creates small

anode/cathode area leading to rapid enhanced attack at the damaged

sites.

Coating metal Substrate metal
Coating metal
Substrate metal
Metallic coatings: (B) Anodic coatings (Sacrificial Barrier) The coating metal is less noble than the
Metallic coatings: (B) Anodic coatings (Sacrificial Barrier)
The coating metal is less noble than
the substrate metal.
i.e. the coating metal is anodic with
respect to the substrate
e.g. the coating of Fe with Zn, Al.
Exposed substrate will be cathodic &
will be sacrificially protected.
Coating metal will form protective
passive layer

It is the use of Cathodic Protection in conjunction with coatings to protect the holidays or voids in the coating

system.

It is the use of Cathodic Protection in conjunction with coatings to protect the holidays or
Methods of application of metallic coatings (A) Electroplating: In this method the object to be

Methods of application of metallic coatings

(A) Electroplating: In this method the object to be coated is made the cathode in an electrolytic cell in which the electrolyte contains the coating metal in the form of ions. M z+ + ze M N.B. In electrolytic cell electrodes have signs opposite to those in a galvanic cell

- + Plating bath cathode Anode
-
+
Plating bath
cathode
Anode

(B) Chemical plating:

In this case the metal deposition can take place by:

(i) Displacement An example of metal plating by displacement is copper on steel according to the following reaction

Fe + Cu 2+ Cu + Fe 2+

More active metal
More active metal
More noble metal
More noble metal
Fe Plating bath Cu 2+
Fe
Plating bath Cu 2+

This method is cheap but the coating is thin and porous and not adhere very well to the steel.

(ii) Chemical reduction (Electroless):

In this case the deposition of the metal is carried out with the aid of reducing agent which is added to

the bath. For example, nickel is plating from an

acidic hypophoshite bath according to

Ni 2+ + H 2 PO 2 + H 2 O Ni + H 2 PO 3 + 2H +

This method gives good throwing power and smooth deposits.

M Plating bath Ni 2+ + reducing agent
M
Plating bath Ni 2+
+ reducing agent

(C) Hot- dip metal coating:

In this process the metallic object is dipped into a bath of the molten coating metal. Intermetallic compounds are formed at the metal-coating interface with the object so that an alloy layer is produced in the region. For example coating steel with zinc by dipping steel in molten zinc (hot-dip galvanization).

is produced in the region. For example coating steel with zinc by dipping steel in molten
is produced in the region. For example coating steel with zinc by dipping steel in molten

(D) Metal spraying

Material Feedstock

(D) Metal spraying Material Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried

Or

(D) Metal spraying Material Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried
(D) Metal spraying Material Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried

Heat Source

(D) Metal spraying Material Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried

Accelerated

Droplet
Droplet

Substrate

Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried out with a spraying
Feedstock Or Heat Source Accelerated Droplet Substrate Coating Metal spraying is carried out with a spraying

Coating

Metal spraying is carried out

with a spraying gun where the

coating metal is melted and projected in the form of drops towards the object surface. In flame spraying, the coating metal

is melted with oxygen-acetylene

flame. In plasma spraying, the coating metal is melted by plasma beam (as ionized argon).

is melted with oxygen-acetylene flame. In plasma spraying, the coating metal is melted by plasma beam

Non-metallic coatings Inorganic coatings

Conversion coating

In this process, the metal reacts with a compound

 In this process, the metal reacts with a compound so that a thin insoluble coatings

so

that a thin insoluble coatings are formed on the metal

surface.

The surface is converted into the coating with a chemical or electro-chemical process.

They are used for corrosion protection, increased surface hardness, to add decorative color and as paint primers. Conversion coatings may be very thin, on

the order of 0.25 m. Thick coatings, up to 50 m,

are usually built up on aluminium alloys, either by

anodizing or chromate conversion.

Non-metallic coatings Inorganic coatings

Conversion coating

(A) Phosphating (Chemical Conversion) Phosphating is usually used on steel before painting.

Phosphate coatings are usually applied to

carbon steel, low-alloy steel, and cast iron. They can also be applied to zinc, cadmium, aluminum, and tin.

can also be applied to zinc, cadmium, aluminum, and tin. H 2 PO 4 - H
can also be applied to zinc, cadmium, aluminum, and tin. H 2 PO 4 - H
H 2 PO 4 -
H 2 PO 4
-
H 2 PO 4 -
H 2 PO 4
-

pH 4.0-5.5

H 2 PO 4 -
H 2 PO 4
-
H 2 PO 4 -
H 2 PO 4
-
Fe 2 Fe 2 Fe 2 Fe 2 + + + + Fe
Fe 2
Fe 2
Fe 2
Fe 2
+
+ +
+
Fe
pH 4.0-5.5 H 2 PO 4 - H 2 PO 4 - Fe 2 Fe 2

insoluble highly adhere Iron

Phosphate

Fe
Fe

Non-metallic coatings Inorganic coatings

Conversion coating

(B) Chromating (chemical conversion) :

coating ( B) Chromating ( chemical conversion ) :  Chromating is used for example on

Chromating is used for example on Zn,

Al and brass. The treatment is carried

out using an aqueous solution of chromic acid or chromate salt where a chromate coating is formed on the metal surface.

where a chromate coating is formed on the metal surface.  The coatings usually have good

The coatings usually have good atmospheric corrosion resistance.

It has good electrical conductivity. It is good base coating for subsequent coatings. Chromate coatings are widely used in protecting common household products and many hardware items with the yellow-brown appearance.

Non-metallic coatings Inorganic coatings

Conversion coating

(C) Oxide Coatings

coatings  Conversion coating (C) Oxide Coatings The oxide coatings are in fact corrosion products which

The oxide coatings are in fact corrosion products which are thin, usually less than 2.5 µm oxide with good adhesion. The oxide treatments are done by heat, chemicals, or

electrochemical reactions.

- + H 2 SO 4 OR H 2 CrO 4 Solutions cathode Al anode
-
+
H 2 SO 4 OR H 2 CrO 4
Solutions
cathode
Al anode

e.g. Anodizing (electrochemical conversion )

Thickening of the naturally occurring oxide layer The anodizing process, usually performed on Al for

protection and cosmetic purposes.

4Al + 6H 2 SO 4 = 2Al 2 O 3 + 6SO 3 + 3H 2 + 6H + + 6e - + 1250 kJ

Thin coatings, 2 µm to 25 µm can be coated on most aluminums. Thick coatings from 25 to 75 µm are more

durable and abrasion resistant than above chemical

conversion coatings. This oxide layer can be made in different colors depending on the dye present in the bath.

coatings. This oxide layer can be made in d i f f e r e n
SEM image of porous alumina anodized in 4 wt.% H 2 C 2 O 4

SEM image of porous alumina anodized in 4 wt.% H 2 C 2 O 4 at 45 V. The pore diameter is ~ 44 nm.

C 2 O 4 at 45 V. The pore diameter is ~ 44 nm.  The
C 2 O 4 at 45 V. The pore diameter is ~ 44 nm.  The

The coatings usually have good atmospheric corrosion resistance.

It has good electrical conductivity.

It is good base coating for subsequent coatings.

Chromate coatings are widely used in protecting common household products and many hardware items with the yellow-brown appearance.

Non-metallic coatings Inorganic coatings

Portland cement coatings

coatings Inorganic coatings  Portland cement coatings  Portland cement can be used to coat the

Portland cement can be used to coat the metal (steel) and minimize

corrosion.

The coatings are usually several centimeters thick.

They often act as a diffusion barrier and raise the pH to more

alkaline levels.

The disadvantage is their sensitivity to mechanical damage.

barrier and raise the pH to more alkaline levels.  The disadvantage is their sensitivity to
barrier and raise the pH to more alkaline levels.  The disadvantage is their sensitivity to
barrier and raise the pH to more alkaline levels.  The disadvantage is their sensitivity to

Non-metallic coatings Inorganic coatings

Vitreous enamels

coatings Inorganic coatings  Vitreous enamels They are hard glassy outside layer and protect the inside

They are hard glassy outside layer and protect the inside metals by acting as an efficient barrier to the corrosive environment

enamel (or vitreous enamel or porcelain enamel in U.S. English) is the colorful result of fusing powdered glass to a substrate by firing, usually between 750 and 850 degrees Celsius.

The powder melts and flows and hardens to a smooth, durable vitreous coating on metal, glass or ceramic.

Celsius. The powder melts and flows and hardens to a smooth, durable vitreous coating on metal
Celsius. The powder melts and flows and hardens to a smooth, durable vitreous coating on metal
Celsius. The powder melts and flows and hardens to a smooth, durable vitreous coating on metal

Non-metallic coatings

Organic coatings

Organic coating : paints, lacquers, varnishes. Coating liquid generally consists of solvent, resin and pigment. The resin provides chemical and corrosion resistance, and pigments may also have corrosion inhibition functions.

pigment. The resin provides chemical and corrosion resistance, and pigments may also have corrosion inhibition functions.
pigment. The resin provides chemical and corrosion resistance, and pigments may also have corrosion inhibition functions.
pigment. The resin provides chemical and corrosion resistance, and pigments may also have corrosion inhibition functions.

Paints are composed of:

1. Pigments

2. Binder 95% of paints are (polymer + oils)

3. Solvent Water based solvent or Oil based solvent

1. Pigments  2. Binder 95% of paints are (polymer + oils)  3. Solvent Water
1. Pigments  2. Binder 95% of paints are (polymer + oils)  3. Solvent Water
1. Pigments  2. Binder 95% of paints are (polymer + oils)  3. Solvent Water

Corrosion preventing painting implies that the metal is covered with a coating system which is able to minimize the corrosion of the metal.

Painting includes the following steps:

of the metal.  Painting includes the following steps: 1) Cleaning the surface (degreasing and removal

1)

Cleaning the surface (degreasing and removal of corrosion products

i. Red lead (Pb 3 O 4 ) as pigment and linseed (ناتكلا رذب) oil as binder.

2)

as scale and rust from the surface). Application of primer: primer must have good adherence to the metal

surface and provide corrosion protection. The following primers are usually used :

ii. Zinc chromate as pigment and alkyd resin as binder.

iii. Zinc phosphate as pigment and alkyd resin as binder

iv. Titanium dioxide (TiO2).

3)

Top paint is designed to protect the primer against the effect of moisture and sunlight as well as give the surface its appearance and colour. The chief components of the top paint are pigment organic binder and colouring material.

Properties to consider the quality of coating

Average thickness of coating

Porosity or continuity Adherence

Uniformity of thickness

Inert or passive

thickness of coating  Porosity or continuity  Adherence  Uniformity of thickness  Inert or