Environmental Degradation Fundamentals · 2020. 7. 10. · Environmental Degradation Fundamentals R. G. Ballinger Professor Massachusetts Institute of Technology. 1 22.39 Reactor

22.39 Reactor Design, Operation, and Safety

Environmental Degradation Fundamentals

R. G. BallingerProfessor

Massachusetts Institute of Technology

1


Outline• Thermodynamics of Corrosion: Pourbaix Diagrams

• Corrosion Kinetics

Polarization Diagrams

Corrosion Rate and Corrosion Potential

Passivation

• Design Implications

2


Thermodynamics

3


Corrosion Cell Schematic

V

i

Anode

Cathode

e- i

Oxidation H Reduction

+-

4


Standard CellV

i

Anode

Cathode

e- i

Oxidation H Reduction

+-H2

Pt

Standard Conditions• 1 Atm• pH = 0• Unit Activity• 25°C

Standard Potential (E0)E0, H = 0

5


Table of Standard Potentials for various Electrode Reactions removed due to copyright restrictions.

Data referenced to Latimer, W. Oxidation Potentials. Prentice-Hall, 1952.

6


Schematic of Corrosion Reactions

2

2

2

2

2

2 2

2 2

2

2

2 2

2 2 2

2 4 4

zaq

nn

zaq

M H O M ze

M nH O MO nH ne

M H O MO H O e

M H O MO H

H e H

H O e H OH

O H O e OH

+ −

− +

−

+

+ −

−

−

+ → +

+ → +

+ → + +

+ → +

+ →

+ → +

+ + →

Metal (M)

H2

M2+

H+

e-

e-

H+H+

H+

H+

H+ H+

Figure by MIT OCW.

2 2

−

+

−

−

+

7


Basic Relationships

2

... ...( ..) ( ..)

(Oxidation)

(Reduction)

2 2 ( )

Q R L m

ne

ne

lL mM qQ rRG qG rG lG mG

Anode

M M neCathode

M ne MH e H g

−

−

+ −

−

+ −

+ + → + +Δ = + + − + +

→ +

+ →

+ →

• G = Free Energy (J/mol)• n = # Equivalents Involved (# electrons)

8


Key Relationships

Pr0

Re tan

( )ln( )

oducts

ac ts

ActivityRTE EnF Activity

= −

ΔG = -nFE

• G = Free Energy (J/mol)• n = # Equivalents Involved (# electrons)• F = Faraday’s Constant (96,500 J/eq)• E = Potential (V)• Eo = “Standard” Potential (V), Potential @ 25°C, Unit Activity, pH = 0• R = Gas Constant (Appropriate Units)• Activity = ~ Concentration (mol/l) for Dilute Solutions

(Activity Coefficient X Concentration for Concentrated Solutions

pH = -log [H+]

9


Pourbaix Diagram: Fe-H2O @ 25°C

Figure removed due to copyright restrictions.

10


Pourbaix Diagram: Cr-H2O @ 25°C


11


Pourbaix Diagram: Ni-H2O @25°C


12


Pourbaix Diagram: Ti-H2O @ 25°C


13


Fe-Cr-Ni System @ 25°C

Corrosion

Passivation

ImmunityImmunity

Passivation

Corrosion

Corrosion

Immunity

Passivation

14


Combined Fe-Cr-Ni @ 25°C

Passivation?

15


Kinetics

16


Schematic “Evans” Diagram

Current Density (A/cm2)

Potential, E (v) vs. SHE

ECorr

(+)

(-)

ER, Cath.

ER, Anode

i0, Cath.i0, Anode. i Corrosion

ηCathodic

ηAnodicM→Mn+ +ne-

M n++ne -→M

H2→2H+ +2e-

2H ++2e -→H2

βCathode

βAnode

17


Schematic of Passive Behavior (Anode)

Current Density (log), (A/cm2)

Potential, E(v) vs. SHE

(+)

(-)

Transpassive

Passive

Active

EPassive

M→Mn++ ne-

iL

iPassive iCritical

18


Schematic of Anodic & Cathodic Interactions-Interplay

Current Density (log), (A/cm2)

Potential, E(v) vs. SHE

(+)

(-) M→Mn++ ne-

iPassive iCritical

EPassive

iL, Anode

ECorr, Passive

Noble Cathode

Active Cathode

ECorr, Active

io, Noble Cathode

il, C1 il, C2 il, C3 il, C4

Flow, TReduction Reaction

19


Key Kinetics Relationships

0

0

log

ln L

L

L

QRT

ii

RT inF i i

DnFi ct

D D e

η β

η

δ−

=

= −−

=

=

• β = “Tafel” Slope• i = Current density• io = Exchange Current Density (A/cm2)• R = Gas Constant (appropriate units)• n = # Equivalents (electrons) transferred• F = Faraday’s Constant (96,500 C/eq)• η = Overvoltage (V)• D = Diffusion Coefficient (cm2/sec)• Do = Constant• Q = Activation Energy (Units consistent with R)• T = Temperature (°K)• c = Concentration (M)• δ = transference #• t = Surface Layer (in solution) Thickness (cm)

20


Key Variables• Temperature

15°C ~ 2X in Rates• Concentrations

M, Hydrogen, Oxygen, Contaminants• Flow Velocity• Potential (Dominated by O2 Concentration)• Compositions (Microstructure)• Stress• Radiation Dose, Dose rate, Radiation Type

21


The Role of ElectrochemicalProcesses in Environmental

Degradation

22


OBSERVATIONS• From an electrochemical point of view all

structural materials are composites.• Electrochemical differences can result in

accelerated electrochemical reactions.• If these reactions occur environmentally

assisted attack may be promoted.• In these situations both anodic and cathodic

processes must be considered.

23


PRECIPITATE/MATRIX CELL

BARE SURFACE

SEGREGATIONIMPURITY

MAJOR ELEMENT DEPLETION

REGION III

REGION I

REGION II

CRACK TIP/METALINTERFACE

METAL

CRACK ENCLAVE

PRECIPITATE AT TIP/METAL INTERFACE

GRAIN BOUNDARY

ANODIC OR CATHODIC PRECIPITATES

PASSIVATING CRACK FLANKS

MASS TRANSFER

MASS TRANSFER

HYDROGEN REDUCTION

DIFFUSION OFMETAL OR IMPURITY

ATOMS TO GRAIN BOUNDARYLOCAL DEPLETIONIN INTERFACE

REGION

METAL DISSOLUTION

Model For EAC Process

24


IMPORTANT PHENOMENA INREGION 1

• Creation of fresh metal by crack propagation.• Galvanic coupling between matrix and

precipitates.• Metal dissolution and other anodic reactions.• Hydrogen reduction or other cathodic

reactions.• Mass transfer to or from the crack enclave due

to diffusion, convection or ion migration.• Crack extension, by mechanical or chemical or

electrochemical means.• Hydrogen assisted crack growth.

25


IMPORTANT PHENOMENA INREGION II

• Precipitation at grain boundaries.• Minor/major element segregation.• Near grain boundary element depletion

or accumulation.• Development of plastic zone due to

crack propagation.

26


IMPORTANT PHENOMENA INREGION III

• Mass transfer into and out of the crack by diffusion, convection and ion migration.

• Oxygen reduction on passive or active crack walls.

27


ENVIRONMENT ASSISTEDCRACKING MECHANISMS

• Stress Corrosion Cracking

• Hydrogen Embrittlement

• Intergranular Attack• Corrosion Fatigue

28


KEY VARIABLES• Grain Boundary Morphology.• Electrochemical Activity of the Grain Boundary.• Fresh Metal Exposure Rate.• Reaction Kinetics.

Film formation rateCorrosion currents

• Galvanic Couples Between Grain Boundary Phases.

• Crack Tip pH.• Crack Tip Potential in Relation to Reversible

Hydrogen Potential

29


TYPICAL PHASESGamma Prime (Ni3(Al,Ti))

Gamma Double Prime (Ni3Nb)Eta (Ni3Ti)

Laves (Fe2Ti...)MC CarbidesM7C3 CarbidesM23C6 CarbidesMnS Inclusions

Oxide InclusionsDelta (Ni3Nb)

30


IMPORTANT PHASECHARACTERISTICS

• Is it anodic or cathodic with respect to other phases or matrix?

• Does it exhibit active or passive behavior?

• What are the kinetics of passivation?

• Corrosion current density?

• Exchange current density?

• Solubility of metal ions?

31


Design Implications

32


Materials Selection Considerations

• Applicability• Suitability• Fabricability• Availability• Economics• Compromise

33


General Material Failure Modes1. Overload

2. Creep Rupture

3. Fatigue

4. Brittle Fracture

5. Wastage

6. Environmentally Enhanced

34


Environmentally Enhanced Failure Modes1. General Corrosion

2. Localized Corrosion

Galvanic

Pitting

Crevice Corrosion

Stress Corrosion Cracking

Hydrogen Embrittlement

Corrosion Fatigue

Intergranular Attack

Erosion-Corrosion

Creep-Fatigue Interaction

35


Key Point• Big Difference Between General & Localized Corrosion

General CorrosionPredictableSlow (Normally)

Localized Corrosion“Unpredictable”Potentially Very RapidCan be Multi-Phenomena (Pitting leading to Crack Initiation)

Significant Design Implications

36


How Do Things “Fail” (Sometimes)• Crack Initiation

Often Multiple Sites (Pitting)Defects “Become”Cracks

Respond to Stress• Multiple Cracks Link

UpHigher Driving Force (K) for “Linked System

• “Main” Crack Propagates to Failure

( )

( )

( , , )

1 1exp

n

gth

ref

C

K f a geometryda C Kdn

Qda K Kdt R T T

K K Unstable

β

σ

α

=

= Δ

⎡ ⎤⎛ ⎞= − − −⎢ ⎥⎜ ⎟⎜ ⎟⎢ ⎥⎝ ⎠⎣ ⎦→ →

37


Crack “History”

Time

Crack Length (a)

a0

UnstableCrack Growth(Exceed KCrit)

Unacceptable NDE Sensitivity

Ideal NDE Sensitivity

“Adequate” NDE Sensitivity ??

38


Indian Point R2C5 Crack

Photos removed due to copyright restrictions.

39


General Design “Rules”

1. Avoid Stress/ Stress Concentrations2. Avoid Galvanic Couples3. Avoid Sharp Bends of Velocity Changes

in Piping Systems4. Design Tanks for Complete Draining5. To Weld or Not to Weld?6. Design to Exclude Air7. Avoid Heterogeneity8. Design for Replacement

Documents

Environmental Degradation Fundamentals · 2020. 7. 10. · Environmental Degradation Fundamentals R. G. Ballinger Professor Massachusetts Institute of Technology. 1 22.39 Reactor