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MAT 373: Surface Degradation and Protection

III. Corrosion testing,


control and prevention
Dr Aleksey Yerokhin

Research Centre in Surface Engineering


Department of Materials Science and Engineering
A.Yerokhin@sheffield.ac.uk
Outline
1. Corrosion Testing
Methods and procedures
Weight loss and gas evolution testing
Electrochemical testing
Cabinet testing
2. Corrosion Control
Monitoring
Inspection
3. Corrosion Prevention
Materials Selection
Change of Environment
Design
Cathodic Protection
Anodic Protection
Protection by coatings

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I. Corrosion testing
Test Methods • Laboratory testing
− Accelerated testing: gives measurable
attacks in a shorter time by using harsher
conditions , e.g. more aggressive
environment, higher E or T. Suitable for
ranking , qualitative comparison and routine
control

− Modelling testing: carried out at realistic


conditions; takes longer than accelerated
tests; requires sensitive measuring
techniques

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Test Methods

• Plant and Field testing: • Pilot plant testing:


real components or testpieces used where conditions cannot be
exposed to industrial or natural modelled by laboratory tests (e.g.
environment expensive installations, with complex
corrosion conditions and great risk of
failure)
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Testing Procedure
Typical testing procedure includes following steps:
• Material selection and pre-treatment
• Surface preparation: ― Measurement of surface area and thickness
― Degreasing
― Weighing
― Masking
• Exposure under controlled conditions: - Oxygen concentration (purging O2)
- Electrolyte pH, C, flow rate (agitation)
- T, RH
• Specimen inspection after exposure (visual, microscopic, chemical analysis)
• Determination of corrosion rate

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Weight loss tests
• Samples are weighted and
immersed in a corrosive solution
• The weight loss is determined
periodically:

Dw(t) = w - wo
• Corrosion rate can be determined
explicitly

• Measurements may be affected by corrosion deposits (careful cleaning is


required before each measurement, which can influence further corrosion
process)

• Localised corrosion cannot be evaluated


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Gas evolution measurements
VH 2 • Method may be preferred when:
- Sample weight is affected by deposition of
corrosion products
- Interpretation of polarisation curves is
complicated
- Corrosion process proceeds with gas
evolution (e.g. corrosion of Mg):
2H2O + 2e−  2OH− +H2
• Under free corrosion, Icorr = Icat
Qa=zFDw  Qc=zF(PVH2/RT)
• Requires delicate gas collection system
• Gas solubility varies with altitude and T
• Can be affected by other chemical reactions
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Electrochemical Testing
Purposes:
• Determine corrosion
potential and corrosion
current
• Characteristic regions
of corrosion behaviour
• Structure of metal-
electrolyte interface

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Electrochemical testing techniques
CATEGORY TEST METHOD
NO applied signal • Open circuit or corrosion potential
• Dissimilar metal corrosion (galvanic corrosion)
• Electrochemical noise analysis
Small-signal polarisation • Polarisation resistance (linear polarisation)
• Electrochemical impedance spectroscopy
Large-signal polarisation • Potentiostatic and galvanostatic polarisation
• Potentiodynamic and galvanodynamic polarisation
Scanning electrode • Potential scans
techniques • Current scans
• Electrochemical impedance spectroscopy scans
Miscellaneous tests • Hydrogen permeation
• Anodized aluminium corrosion test
• Paint adhesion on a scribed surface
• Critical pitting temperature, etc

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Tests with NO applied signal
1. Open Circuit Potential
Potentiostat
E = OCP A
Ie = 0
RE

WE CE

• Potential between WE and RE adjusted to keep external current Ie = 0 (open


circuit condition). OCP vs immersion time is monitored and plotted

• Instabilities in OCP behaviour reflect changes in surface state (passive film


formation and breakdown, deposition and dissolution of corrosion products)

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2. Electrochemical noise
ZRA • Corrosion process generates low-frequency (<1 Hz) and
EECN A low-amplitude random fluctuations (noise) of current
IECN (1 nA to 10 μA) and potential (0.1 μV to 10 mV) signals
RE • Pattern of these signals can be used to evaluate
corrosion activity

WE1 WE2 • ECN test uses 3 electrodes: 2 identical working


electrodes (WE1 and WE 2) and reference electrode
(RE)
• WE1 and WE2 coupled through a zero resistance
ammeter (ZRA) to measure current noise IECN
• WE1 and RE connected to a potentiometer measuring
potential noise EECN
• EECN and IECN analysed in both time and frequency
domains

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Tests under Small Signal Polarisation
1. Linear polarisation resistance Rp
• In a limited potential range (up to ±20 mV)
around Ecorr, the relationship between DE and
Die is linear
• The curve slope is given by Stern–Geary
equation:
𝑑𝐸 𝑏𝑎 × 𝑏𝑐
𝑅𝑝 = =
𝑑𝐼𝑒 2.3(𝑏𝑎 + 𝑏𝑐 )𝐼𝑐𝑜𝑟𝑟

• By polarisation to about ±10 mV from Ecorr, the slope DE/DIe can be


determined
• Icorr can be calculated from the above equation when the Tafel constants ba
and bc are known

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2. Electrochemical impedance spectroscopy
• EIS is based on frequency response (FR) analysis of
linear time-invariant (LTI) systems
• FR is spectrum response of system to a small input
signal of varying frequency

Input signal • Transfer Function H(s) can be determined by


identifying characteristic Fourier transforms (time
domain) to corresponding Laplace transforms
(frequency domain)
𝐸(𝑡,𝑗𝜔) 𝑌(𝑠)
𝑍 𝑡, 𝑗𝜔 = ≡ 𝐻 𝑠 = 𝑋(𝑠)
𝑖(𝑡,𝑗𝜔)

• FR operates with two terms: Impedance Magnitude


Output signal |Z| and Phase Angle :
𝑍 𝑗𝜔 = |𝑍|𝑒 𝑗𝜃

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Analysis of impedance data
FitResult FitResult

-1250 104

Re Rct
Re – electrolyte resistance

|Z|
103
-1000
Rct – charge transfer
Cb

-750
102
10-3 10-2 10-1 100 101 102 103 104 105 106
resistance
Frequency (Hz)
Cb – barrier capacitance
Z''

-500 Element Freedom Value -75


Error Error %
Re Fixed(X) 100 N/A N/A
Rct Fixed(X) 1000
Phase angle
-50 N/A N/A • Polarisation resistance:
-250
Cb
Re
Fixed(X)
Rct
1E-06
-25
N/A N/A
Rp = Re + Rct
0 Data File: FitResult 0
0 250 500 750 1000 1250 10-3 10-2 10-1 100 101 102 103 104 105 106
Circuit Model File:
Z' Frequency (Hz)
Mode: Run Simulation / Freq. Range (0.001 - 1000000)
Maximum Iterations: 100
• Impedance data presented as Complex (Z’’ vs Z’) and 2 Bode plots (|Z|
Optimization Iterations: 0
and vs w)
Type of Fitting:
Type of Weighting:
Complex
Calc-Modulus

• A model (equivalent circuit) is adopted to fit the data


• Obtained values of circuit components are used to evaluate the
resistance to corrosion process Rp
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Tests under Large Signal Polarisation
1. Potentiodynamic corrosion tests
1
Potentiostat
E = E(t) A 0.8

Ie = I(t)
0.6 (i) (ii)
RE

E (V)
0.4

WE CE 0.2

0
• Potential between WE and RE is swept and 10-8 10-7 10-6 10-5 10-4
Log I (A cm-2)
external current Ie between WE and CE recorded
• 2 scan types can be performed: (i) Single scan from below OCP in anodic direction (ii)
two separate scans from OCP in cathodic and anodic direction
• Cyclic forward and reverse scans possible (e.g. to determine pitting potential Ep)
• Both anodic behaviour and corrosion rate can be determined

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Analysis of polarisation curves
• In general, Ecorr and icorr can be determined by
(a)
extrapolation of linear parts of polarisation curves if
both cathodic and anodic reaction are under activation
control (Fig a)
• Tafel slopes are usually observed at || = 0.1…0.25V:
2.3𝑅𝑇
𝑏=
𝛼𝑧𝐹
• Stern-Geary analysis is valid:
(b)
𝑏𝑎 × 𝑏𝑐
𝑅𝑝 =
2.3(𝑏𝑎 + 𝑏𝑐 )𝐼𝑐𝑜𝑟𝑟
• If Tafel region cannot be resolved on one of the
curves (e.g. ba), extrapolation of bc towards Ecorr is
considered (Fig b)

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Analysis of polarisation curves II
• Possible deviations include:
(c)
(c) 1. Cathodic reaction is diffusion
and anodic – activation controlled:
𝑏
Icorr = Ilim 𝑅𝑝 = 2.3𝐼𝑎
𝑙𝑖𝑚

2. Cathodic reaction is activation


controlled; the metal is passive:
𝑏
Icorr = Ip 𝑅𝑝 = 2.3𝐼𝑐
𝑝
(d)

(d) Cathodic curve is irregular; the


metal is passive:
Icorr = Ip

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Cabinet testing
Salt-spray/fog corrosion tests:
• Carried out in cabinets for a
specified period of time
• Quality control in manufacturing
• Relative performance comparison
of metals and coatings to a
standard
• Not intended for simulation of a
particular environment or service
condition

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Salt-spray/fog corrosion tests
• Main parameters: • Two main test types:
– Electrolyte (composition, pH, – Static (only Duration is varied)
specific gravity)
– Cyclic (Temperature and Relative
– Temperature
humidity are varied in cycles)
– Relative humidity
– Duration

• Main criteria:
– Surface appearance
– Time to failure

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II. Corrosion control
Monitoring and inspection
• Justification:
– Periodic maintenance and servicing is more cost
effective than repair, replacement and/or dealing
with aftermath
• Critical cites:
– Obstructions and Irregularities, e.g. sharp pipe
bends and bore size changes (local changes of flow
direction, velocity, turbulence and erosion)
– Crevices and Areas of stagnant water (crevice or
deposit corrosion)
– Dissimilar metal junctions (galvanic corrosion)
– High Local Stresses, Temperature or Pressure
(stress corrosion cracking, thermally induced
corrosion)

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III Corrosion prevention
Materials selection
• General guideline for materials selection is maximum corrosion resistance.
This can be achieved by utilisation of 2 effects:
(a) Immunity (b) Passivity
Cu Ti

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Inspection and monitoring methods I
A. Indicating the state of the plant
1. Visual inspection (at all places accessible at production stops)
2. Leak detection
― Thermography
― Acoustic emission
― Hole drilling up to corrosion allowance

3. Radiography of corrosion defects


4. Eddy current (to detect pits, cracks, intergranular and selective corrosion)
5. Ultrasonic techniques
6. Pipeline Inspection Gauge (PIG) devices (ultrasound, eddy current, spring-
loaded calliper, magnetic flux and induction)
7. Field signature method (FSM) (test potential differences in a number of points
that depend on material thickness reduction)

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Inspection and monitoring methods II
B. Indicating plant function and possible corrosion in action
8. Weight loss coupons placed in process environment and removed after a
certain time
9. Electrical Resistance (ER) probes (DU between 2 points in the probe increases
with corrosion)
10. Linear polarization resistance (LPR) probes (2- or 3-electrode; DC or AC)
measure instantaneous corrosion rates
11. Acoustic emission probes measure ultrasonic waves generated by stress
corrosion cracking, corrosion fatigue and deformation of material
12. Other methods:
― Potential measurements using conventional voltmeters and reference electrodes
― Hydrogen probes measure H2 evolution and adsorption rates
― Process fluid analysis (e.g. for presence of Fe2+)

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Materials of choice
Environment Material
Nitric acid Stainless steels (Fe-Cr-Ni)
Caustic solutions Ni
Hydrofluoric acid Monel (Ni-Cu)
Hot hydrochloric acid Hastelloys (Ni-Mo-Cr-Co-Fe)
Chlorimets (Ni-Mo-Cr-Fe)
Non-staining atmospheric exposure Al
Dilute sulphuric acid Pb
Distilled water Sn
Hot, strongly oxidizing solutions Ti
Concentrated sulphuric acid Steel (Fe-C)
Ultimate resistance Ta

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Unalloyed and low-alloy steels
Unalloyed (carbon) steels
• Resist fairly well to concentrated H2SO4 (>70%, stagnant, at room T)
• Alkaline solutions, e.g. NaOH and KOH, without contaminants
• Used in tanks, pipes, transport containers and production equipment
• Risk of Stress Corrosion Cracking (SCC) in hot acids and alkalis
Special low-alloy ‘weathering’ steels
• resist atmospheric corrosion but little effect on soil and aqueous corrosion
% Ni Corrosion rate, mm/y % Cr Corrosion rate, mm/y • CO2 corrosion
strongly affected by
0 0.9 0 0.9 alloying elements,
3 0.1 2.25 1.25 e.g. Ni & Cr (Table)
5 0.075 5 0.525
9 0.05 9 0.04
• Increasing strength
increases risk of
12 0
SCC!
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Cast irons
Low-alloy cast irons: – behave similar to low-alloy steels
– higher SCC tendency for grey cast irons
High-alloy cast irons: – very good general corrosion resistance:
– draining pipelines, pumps, valves, processing equipment
a) silicon iron (14.5-18 Si)– form SiO2 protective film
b) cast iron with Ni and/or Cr.
Material % Alloying elements
Durasid 14.5 Si, Mo
Durichlor 14.5 Si, Mo, Cr
Thermisilid 18 Si
Ni-Resist 1 15 Ni, 6 Cu, 2 Cr, 2.8 C
Ni-Resist 2,3 20-30 Ni, 2-3 Cr 2.0-2.6 C
Guronit G52 25-30 Cr
AISI 446 L 23-27 Cr, 0.35 C, 0.25 N
Example of SCC in cast iron: cracks driven by graphite
inclusions. www.element .com

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Stainless steels
• Cr >11% - passivation by Cr2O3 film prevents corrosion and high-T oxidation
• Ni - stabilises austenite
• Cu, Mo, Ti, Si - improve corrosion resistance to selected acids
• N - increases strength and stabilises austenite
• C <0.03%, Nb - prevent chromium carbide precipitation (intergranular corrosion)

Martensitic (0.25%C) - higher strength but moderate corrosion resistance


- relatively good resistance to cavitation, erosion & wear
• Ball bearings, turbine blades, valve guides, tools, cutlery, and surgical instruments
Ferritic (<0.1%C, a-Fe) - non-hardenable, ductile and modetalely weldable
• 16–18% Cr - good resistance to atmospheric corrosion and nitric acid
• 18–27% Cr - resist oxygen and sulphur at high temperature
• Unpainted automobile parts, HNO3 storage tanks, processing equipment
Austenitic (18% Cr-9% Ni) - more corrosion resistant, ductile and weldabile than Cr steels
• Process industry, food manufacture, kitchen and architecture

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Stainless steel grades
AISI Composition/Type s0.2 MPa d%
405 13Cr F 250 20
M 490 16
430 17Cr F 250 18
444 18Cr2Mo F 340 25
- 16Cr5Ni1Mo M-F 620 15
- 23Cr4Ni(N) F-A 400 25
- 22Cr5Ni3Mo(N) 418 25
- 25Cr7Ni4Mo(N) 550 25
304 18Cr9Ni A 210 45
304LN 18Cr9Ni(N) 290 40
316 17Cr12Ni2.5Mo A 220 45
310S 25Cr20Ni A - -

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Steels for different environments
• Reducing acids, very strong oxidizing acids and alkalis
- Stable passivation for most stainless steels - mainly uniform corrosion
- pitting, crevice, intergranular corrosion or SCC are also possible
• De-ionized & distilled water
- any steel (although intergranular corrosion in sensitized 18-9 possible at >100oC)
• Tap (hot & cold) & fresh water
<200 mg/l Cl 18-9
200-500 mg/l Cl 17-12(Mo)
>500 mg/l Cl Special steels
• Waste water systems (cold)
<300 mg/l Cl 18-9(Mo) or 17-12
• Swimming pools
high Cl contents Mo-alloyed steels
• Sea water (Cl + bacterial slime layer)
Unsensitised (left) and Sensitised (right) 18-9
- High risk of corrosion for most stainless steels (AISI 304) steel. Precipitation of CrxCy occurs at
- Welds particularly vulnerable grain boundaries at 425-815 oC
20Cr25Ni4.5Mo1.5Cu
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Nickel alloys
• Main alloying elements:
Cu, Cr, Mo, W, Nb, Ta
• Most corrosion-resistant alloys for
long-term protection in aggressive
environments
• More expensive than stainless steels
• Good for high flow rate but may
develop deposit/pitting corrosion in
stagnant sea water

Monel K-500 in the hot rolled condition. Structure: nickel-copper solid solution. Variation in shade of
grains is the result of variation in grain orientation. Glyceregia. x100
W.L. Mankins. ASM Handbook, (2004) V 9 816

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Applications of nickel alloys
Alloy / Composition Applications
Monel 500 / High-strength components, e.g. pump & propeller shafts,
66Ni30Cu3Al1Fe impellers, valve components, for ships & oil/gas production
Incoloy 825 / Chemical processing, oil & gas well piping, acid production,
42Ni22Cr30Fe3Mo2Cu1Ti nuclear fuel reprocessing, pickling equipment
Hastelloy C22 / Suitable for welded or cold-worked components, welding
59Ni22Cr13Mo3Fe3W consumables
Hastelloy C276 / Outstanding resistance to oxidizing & reducing media &
59Ni16Cr16Mo5Fe4W local. corr. Chemical and petrochemical, organic chloride
processes, pulp & paper industry, food processing, flue gas
desulphurization
Inconel 625 / High-strength components in seawater, oil/gas production
63Ni22Cr9Mo2Fe4(Nb+Ta) (H2S & S >150oC), flue gas/flue gas desulphurization, flare
stacks offshore, hydrocarbon processes

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Copper alloys
• Eo = 0.34V : - Corrosion resistance by immunity (especially in reducing media)
- Cathodic reaction of H+ reduction is impossible
• pH 7…13: - Passivity region provides stability in atmospheric conditions & alkalis
- But varying liability to selective, erosion corrosion and SCC
- Sensitive to sulphur & ammonia containing environments (H2S, NH3)
• Applications: - Roofing, hot & cold water piping, heat exchangers, valves, fittings,
castings and housings
Wrought Cu alloys Corrosion Resistance Index
(brasses) SCC Selective Erosion • Wrought alloys – mainly
brasses (Zn, Ni, Al)
Cu 5 5 1
Cu(10-40)Zn 4-2 4-2 2-3 • Cast alloys – mainly bronzes
(Sn, Al, Ni, Zn)
Cu(40-36)Zn (3-1)Pb 1-2 1-2 3
Cu(10-30)NiFeMn 5 5 4 • Mechanical properties
s0.2 =60-250 MPa, sb =150-700
Cu(12-18)Ni(20-24)Zn 4 4 4
MPa (45…160HB), d= 3-20%

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Aluminium alloys
Eo = -1.66 V - rely upon dense and continuous passive film Al2O3·3H2O
- often enhanced by electrochemical oxidation (anodising)
- corrosion involves H+ reduction but with high overvoltage
pH = 5.5…10 - efficient only in atmospheric conditions & reasonably pure water
- colourless and non-poisonous corrosion products
- pitting corrosion in presence of Cl- ; catalysed by impurities
Properties: - High electrical & thermal conductivity
- Low density (2.7 g/cm3)
- High strength/weight ratio
- Formability: casting, rolling, drawing
and extrusion, welding
Alloys: - Cast (Al-2…25%Si)
- Wrought: Zn, Cu – strength, Li -  density
Mg, Mn – corrosion resistance
Microstructure of hypereutectic Al-18% Si: coarse primary Si grains in Al-12%5Si eutectic matrix; some α-Al dendrites.
R Wang & W Lu, in Electrolysis, Intech publ. (2012)

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Applications of wrought Al alloys
AA Grade / sb Atm. Corr. Application fields
Composition (MPa) Resistance
1050 55–135 Very Good Apparatus, panels, goods, hardware, food
99.5% Al industry, rivets, packaging
2014 >370 Fair Machined components, machinery, fasteners
Al 4Cu 1Si 1Mg
3003 90–175 Very Good As AA1050 plus components of vehicles &
Al 1Mn accessories
5083 275–345 Very Good Apparatus, shipbuilding, components of vehicles
Al 4.5Mg 1Mn & accessories
6351 >200 Good Conctruction, panels, machined components,
Al 1Si 1Mg electro–mechanical, vehicles & accessories
7005 200–350 Good Machined components, electro–mechanical,
AlZn4Mg1 vehicles & accessories, tools, machine making

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Titanium alloys
Eo = -1.63 V - rely upon passivation by TiO2 film
pH = 1…13 - excellent corrosion resistance in a wide range of environments
- but very sensitive to hydrogen embrittlement
Properties: - Low density (4.5 g/cm3)
- Very high strength/weight ratio
- High ductility & fracture toughness
- Low thermal conductivity
- Rolling, extrusion, casting, welding
- Difficult to machine
Applications: - Due to high cost limited only to
highly demanding applications
- aerospace, nuclear, defence
- chemical and biomedical Typical microstructure of annealed a+b Ti alloy
(Ti-6Al-4V): a-Ti matrix (bright phase) with dark
Alloys: - a-Ti; a+b-Ti, b-Ti alloys (Al, V, Nb) inclusions of b-Ti (Ti-Al-V solid solution)

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Change of Environment

4 ways to change environment

Add Inhibitors
Change Change Change
Temperat Flow Oxidiser
ure velocity content
Not
Passivating
passivating

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Inhibition mechanisms: 1. Passivators
E
a) Oxidising inhibitors (CrO42-, Cr2O72-, NO2-)
w – Without inhibitor, metal exhibits active-passive behaviour
and cathodic reaction is activation controlled (strong acids)
cr – Inhibitor addition increases oxidiser concentration to shift
wo cathodic curve up to intersect with anodic curve in the
passive state
E b) Anodic passivating inhibitors (NaOH, Na2PO4,
w Na2SiO3, Na2B4O7)
– Without inhibitor, metal exhibits active behaviour and
wo cathodic reaction is diffusion controlled (aqueous solutions)
– Inhibitor addition changes metal behaviour to passive,
without affecting cathodic behaviour

Log i w – with inhibitor wo – without inhibitor


cr – critical concentration of inhibitor
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Inhibition mechanisms:
2. Not passivating inhibitors
E
wo
wo
w w w
w – with
wo inhibitor
wo – without
(a) (b) (c) inhibitor
Log i
• Affect only kinetics of electrode reactions
a) Cathodic inhibitors, e.g. hydrazine reduces O2 concentration by chemical reaction:
N2H4 + O2  N2 + 2H2O
b) Anodic inhibitors, e.g. acid pickling solutions increase anodic polarisation by adsorption
c) Double acting inhibitors, e.g. organic substances reduce both reaction rates by
adsorption

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Corrosion prevention by design
Main design rules:
1. Sufficient corrosion allowance
2. Easy to replace most liable to corrosion components
3. Easy drainage with sufficient supply of air
4. Easy inspection and cleaning
5. Avoid hot or cold spots

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Corrosion prevention by design (II)
Main design rules (contd):
6. Account for surroundings to minimise consequences
7. Shift the attack to less critical places
8. Simple geometry (avoid heterogeneity and sharp changes)
9. Use appropriate materials for flow velocities
10. Adjust pressure gaskets

improper proper improper proper

electroplated painted

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Cathodic protection
• Main principle: application of
external current Ie to force Ecor
down to the immune region Ec or
below pitting potential Epit
• Ie can be produced in two ways :
a) Sacrificial anode (less noble
material) connected to the
structure to be protected
b) Impressed current method:
External current source used
between the structure and the
anode

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Anodic Protection
E

DEa

Dicorr
Log i

• Main Principle: metal polarisation in anodic direction to lift Ecorr up to the


passive region Epas
• Low protection current required makes anodic protection economical
• All surfaces are uniformly protected
• Should be used with care: overpolarisation may lead to pitting corrosion

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Corrosion protection by coatings

• Main mechanisms of corrosion protection by coatings:


i) Barrier effect, where any contact between the corrosive medium and the metallic
material is prevented (organic coatings, paints, ceramic coatings)
ii) Cathodic protection, where the coating material acts as a sacrificial anode (Cd, Zn,
Al)
iii) Inhibition/passivation, including cases of anodic protection (anodising, Cr, Ni, Sb,
Pb, conversion coatings)

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Coating methods
• Electroplating
• Hot dipping
• Spray
• Conversion Hot dip galvanising process Structure of hot-dip Zn coating

• Sol-gel
• Vapour deposition
• Diffusion
• Brushing
Plasma spray coating process Structure of sprayed Zn coating

MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
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