Beruflich Dokumente
Kultur Dokumente
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 2
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 3
Yerokhin
Test Methods
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 5
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 8
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 9
Yerokhin
Tests with NO applied signal
1. Open Circuit Potential
Potentiostat
E = OCP A
Ie = 0
RE
WE CE
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 10
Yerokhin
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 11
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 12
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 13
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''
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 15
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)
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 16
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 17
Yerokhin
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 18
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 19
Yerokhin
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)
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 20
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 21
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 22
Yerokhin
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+)
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 23
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 24
Yerokhin
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!
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 25
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 26
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)
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 27
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 - -
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 28
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 29
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 30
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 31
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%
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 32
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)
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 33
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
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 34
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)
07/03/2014 MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A Yerokhin 35
Change of Environment
Add Inhibitors
Change Change Change
Temperat Flow Oxidiser
ure velocity content
Not
Passivating
passivating
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 36
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 38
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 39
Yerokhin
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
electroplated painted
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 40
Yerokhin
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
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 41
Yerokhin
Anodic Protection
E
DEa
Dicorr
Log i
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 42
Yerokhin
Corrosion protection by coatings
MAT 373 Corrosion. Part III: Corrosion Testing, Control & Prevention, by Dr A
07/03/2014 43
Yerokhin
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
07/03/2014 44
Yerokhin