Stress Corrosion Cracking and Fatigue:

mechanical load (tension) + Corrosive environment

When does Stress Corrosion Cracking (SCC) occur ?

Simultaneous influence of tensile stresses and aggressive environment Only one of these parameter does not induce crack growth
- Composition - Heat treatment - Microstructure - Surface condition

SCC is a system not a material problem

Material
Corrosion SCC

Fatigue

- Design - Mechanical bulk stresses - Internal stresses Production

Stresses

Environment

- Aggressive media - Temperature - Potential /Current - Microfluidics

2

Stress Corrosion Cracking: process steps

Definition: Stress Corrosion Cracking is the initiation and slow growth of cracks under the simultaneous influence of tensile stresses and aggressive environment SCC processes is divided in three phases: 1. 2. 3. Incubation Crack growth Breaking

Incubation time is the most important aspect for the life time of a component SCC is from all the corrosion attack, the one resulting in the fastest damage of materials

Type of crack propagation

Intergranular: Attack at the grain boundary Transgranular: attack through the grains

SCC: important features

Materials breakdown happens at macroscopic scale, without deformation and perpendicular to the stress direction No measurable material removal No visible corrosion products

In most of the SCC failure, corrosion initiation is difficult to detect

Types of SCC corrosion attack

There is a whole range of attack ranging from: at one end the purely intergranular attack and on the other end the brittle fracture
Corrosion Tension Brass NH3 18/8 CrNi Cl Mg-Al Cr2-4/ Cl Ti Steel H2O

Intergranular corrosion

Steel NO

Al-Zn-Mg Cl

- CH OH 3

Stress deformation induced Metal dissolution

Defined Crack direction Crack evolution Controlled by deformation

Adsorption induced brittle fracture

small

crack propagation rate

large
6

Brittle fracture

High strength

SCC: 2 main mechanisms

For small until medium crack propagation rates:

Type 1: anodic metal dissolution accelerated by stress

It is an electrochemically controlled processes with following model:
metal Passive oxide active crack tip passive crack wall
diffusion, convection

crack propagation

Plastic deformation Crack electrolyte

Cathodic partial reaction 7

electrolyte

Type 2: adsorption induced brittle fracture

For fast crack propagation rates, the cathodic reactions plays a larger role (anodic dissolution is too slow) At the crack tip, adsorbed or species diffused in the metal weaken the metallic binding forces
electrolyte shear plane

Adsorbed anions

the most dangerous species: hydrogen causes embritlement HIC (hydrogen induced cracking)
metal

crevice plane From adsorption weakened metal bounds 8

SCC: summary of mechanisms

Anodic SCC Dominated by anodic metal dissolution Cathodic SCC Dominated by H2 production
(also for example from cathodic deposition of protecting layers)

Crack propagates through accelerated dissolution due to applied stress

Crack propagates because of hydrogen embritlement due to hydrogen diffusion

Stainless Steel Cracks are propagating from the surface

High strength steel Crack are also generated inside the material

SCC: typical crack evolution

Not a single clearly defined crack !
Near the surface: Secondary crack with ramification
Ramified crack propagation observed on the metallographic cross section

ca. 50 m

ca. 2 mm

10

Example: fractographic analysis of broken cable

- Sem investigation of the fracture surface Brittle (fragile)

Ductile

Intergranular

11
Empa unterwegs Sion, 09. 11. 2006

SCC: metallographic investigation

Example of SCC on coated (thick oxide) aluminum - Presence of intergranular attack near the main crack - Detection of Cl- in the material by EDX Damaged surface eloxal layer EDX analysis of internal

Intergranular attack

12

Model experiments: aspects of fracture mechanics

Fracture mechanics can give useful information on crack propagation rates in technical application It is based on consideration of macroscopic parameters like crack length, applied tensile stress (S), sample geometry
S S

Assumption: test are always performed on notched (depth:d) specimens (width:w) Initial crack geometry + environment critical applied stress
W d

W
d

S
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Experimental characterization of SCC

Crack propagation rate as a function of applied stress intensity
When the critical load for SCC is reached (KIscc) , a fast increase of the crack propagation rate Is observed Log (crack propagation rate d / t) Schematic evolution of crack propagation for SCC

Domain 1:

Domain 2:
Constant SCC propagation rate typical for the influence of electrochemical control

Domain 3 and 4: If the KIc is reached, the standard

brittle fracture is taking place as in absence of aggressive environmental influence

Applied stress K

14

Important parameters for the evolution of SCC

Incubation (crack formation) Chemical or mechanical damage of the passive layer Critical factors are electrochemical nature (temperature, electrochemical potential, aggressive ion concentration) and the influence of stresses on the passive film Crack propagation Metal dissolution followed by repassivation Critical factors is the ratio of the tensile deformation and the repassivation rate at the crack tip
15

SCC: influencing parameters

1) Materials
Susceptibility can be controlled inadequate heat treatment resulting in sensitization (chrome depletion at grain boundaries) for example is extremely detrimental Alloying of nickel is beneficial (around 20 %)

Example: CrNi wires in boiling MgCl2 (154C)

Austenitic structure is more resistant then ferritic

Time to failure (h)

Weight % Nickel

16

SCC: influencing parameters II

Molybdenum decrease the SCC susceptibility in the critical Ni concentration domain mainly in increasing the critical KISCC threshold
Critical KISCC (MN / m1.5) Weight % molybdenum

Example: CrNiMo Steel With 15.5 21% Ni 22 %Cr In aerated NaCl solution (105C)

17

SCC: influencing parameters III

Temperature
At room temperature, SCC is usually not observed in chloride containing environment (seawater or similar environment )

Be careful with acidic environments (crevice condition) where SCC is occurring also at room temperature

Aggressive ions
Temperature ( C)

SCC (initiated at pits) No SCC after 10000 hours exposure

CrNi Steels Chloride anions

Cl- concentration in aqueous electrolyte (ppm)

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Measures to avoid SCC

Avoid stresses on the material - Internal stresses can be reduced with adequate heat treatment - External stresses are often decreased just by design consideration (avoid having applied stresses on welds !)
To avoid right design

Remove aggressive environment (special care have to be taken to crevice conditions)

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Corrosion - Fatigue: cyclic loading

Special case of Stress Corrosion Cracking (SCC) Applied stress is not constant but experiences cyclic variations aggravated SCC attack
Metallographic cross section

Much more materials and environments are concerned

Transgranular crack propagation

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Corrosion Fatigue: mechanisms

Factors influencing corrosion-fatigue processes are similar to SCC - The cyclic loading can induce constant depassivation
Initiation sites for corrosion fatigue
Passive layer

- Interaction between gliding planes and electrolyte plays a key role - At the induced micro notches, additional gliding and accelerated corrosion is induced

Corrosion susceptible area Gliding plane

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Whler curves in the case of corrosion - fatigue

Corrosion rate is dependent on the cycle number and amplitude
This has to be taken into account for fatigue-corrosion
Stress amplitude 1. smooth surface Air, RT 2. notched surface Air, RT 3. smooth surface Conc. NaCl 4. notched surface Conc. NaCl

The Whler curves display the failure time in relation to cycle number and stress amplitude

Important to note: surface defects (notches) plays a tremendous role in the life of a component exposed to fatigue condition

Cycle number

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Fatigue: experimental setups

The specimens used were CT-specimens (CT: compact tension) The geometry of the specimen is given as relative dimensions of the width W

The specimen made from 7075-T651 had a width of 60 mm and a thickness of 10 mm ( with W = 40 mm and B = 3.63mm). The initial notch depth a0 was 17 mm or 32 mm. The specimen were loaded by a pair of pin loads at x=0, y=0, z=0.225W in the z direction. The loading was a sinusoidal constant amplitude history with a frequency of 83 or 54 Hz. The CT-specimen was equipped with a clip gauge at the mouth of the notch. The crack length was monitored optically by two traveling microscopes, fixed to the test bed and allowing to measure both surface crack lengths, on the front and on the back face. 23

Some important parameters and relations

a a0 Keff da/dN crack length, crack depth, crack size original crack size, initial crack length

effective stress intensity factor range fatigue-crack-growth rate measured in constant amplitude tests

R Pmax Pmin

load ratio := Pmin/Pmax or Kmin/Kmax maximum load on the C(T) specimen minimum load on the C(T) specimen

Kmax Kmin

maximum stress-intensity factor minimum stress-intensity factor

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Used aluminum alloy: 7075

Element Si Silicon Fe Iron Cu Copper Mn Manganese Mg Magnesium Cr Chromium Zn Zinc Ti Titanium Ni Nickel Others, each Others, total Al Aluminum A 0.06 0.30 1.70 0.03 3.10 0.18 5.60 0.03 <0.01 <0.01 Balance Measurements in weight % B average 0.06 0.06 0.30 0.30 1.70 1.70 0.03 0.03 3.10 3.10 0.18 0.18 5.60 5.60 0.03 0.03 <0.01 <0.01 <0.01 <0.01 Balance Balance Specification in weight-% 0.40 0.50 1.2 - 2.0 0.30 2.1 - 2.9 0.18 - 0.28 5.1 - 6.1 0.20 0.05 0.05 0.15 Balance Remarks

The T651 temper is a solution heat-treated, quenched, 1.5 to 3% controlled stretched, and artificially aged condition with a maximum static strength. Second phase particles in these alloys are usually categorized into three groups: - Large (approx. 1 to 30 m) intermetallic particles formed during solidification by
combination of impurities (Fe, Si) and solute elements: Al12(Fe,Mn)3 Si and Al7Cu2Fe - Smaller (approx. 0.3 m) dispersoid particles formed by solid state precipitation of Cr and Mn at temperatures above 425C: Al20Cu2Mn3 - Fine (0.5 nm - 10 nm) precipitates, containing solute elements. Formed during quenching or aging: Al2CuMg 25

Al oxidation process as function of atmosphere

- Oxide film growth will occur very rapidly (formation of the 5-6 nm passive film in a few millisecond in air) in air with a slight humidity related acceleration - Even in Nitrogen atmosphere, a nm-thick oxide will form in millisecond - In fine vacuum (high vacuum), the formation is then obviously hindered and only monolayers of oxygen will be chemisorbed on the surface

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7075-T651: crack propagation in vacuum

The experimentally measured results (with the fitted parameters) for 7075T651 are shown below with the propagation rates (da/dN) and the onset of under critical crack growth
10'000.000

crack growth rate in 7075-T651 in fine vacuum

1'000.000

100.000

10.000 SCVA, R = 0.1, Delta K up SCVF, R = 0.1, Delta K up SCVA, R = 0.1, Delta K dw SCVB, R = 0.1, Delta K dw SCVB, R = 0.3, Delta K up SCVD, R = 0.3, Delta K up SCVB, R = 0.3, Delta K dw SCVC, R = 0.5, Delta K dw SCVC, R = 0.5, Delta K dw SCVC, R = 0.5, Delta K up SCVC, R = 0.5, Delta K up SCVE, R = 0.5, Delta K dw SCVE, R = 0.5, Delta K up model with slip

1.000

da/dN [nm/cycl

0.100

0.010

0.001 1 10

Delta K eff [MPam^0.5]

100

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7075-T651: crack propagation in nitrogen

10'000.000

crack growth rate in 7075-T651 in purified nitrogen

1'000.000

100.000

10.000

1.000

SCNC, R=0.1, f = 54 Hz SCND, R=0.3, f = 54 Hz SCNE, R=0.3, f = 83 Hz

da/dN [nm/cycl

0.100

SCNF, R=0.5, f = 54 Hz SCNG, R=0.5, f = 54 Hz SCNF, R=0.5, f = 83 Hz

0.010 model with d_ox

0.001 1 10

Delta K eff [MPam^0.5]

100

- In nitrogen, the critical stress intensity Keff to initiate fatigue crack growth is decreased and the propagation rates in the undercritical domain is also faster - There is clearly a material-environment combination in this process

28

7075-T651: crack propagation in air

10'000.000

crack growth rate in 7075-T651 in humid air

1'000.000

100.000

10.000

1.000 S0LA, R=0.1, Delta K up SCVA, R=0.15, Delta K dw SCLB, R=0.3, Delta K up SCLB, R=0.3, DeltaK dw SCLC, R=0.5, Delta K up SCLC, R=0.5, Delta K dw new model with d_ox new model without d_ox 0.010

da/dN [nm/cycl

0.100

0.001 1 10

Delta K eff [MPam^0.5]

100

- In air, the critical stress intensity Keff to initiate fatigue crack growth is similar to nitrogen but the propagation rate is then slightly higher - The environmental component is related to the presence and thickness of passive film that is constantly broken at every cycle and reforms

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Summary: role of passive oxide film on fatigue

10'000.000

Crack Growth in 7075-T651 in Different Environment

1'000.000

100.000

10.000

1.000

0.100

da/dN [nm/cycle

Vacuum Purified Nitrogen 0.010 Laboratory Air

0.001 1 10

Delta K_eff [MPam^0.5]

100

- The fatigue crack propagation rate increase as function of stronger oxidizing conditions can be seen by overlapping the curves measured in different environments

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Passivation process and stress distribution

31

Short summary: Al Fatigue-corrosion

The empirically found crack growth rates are understood as the superposition of these mechanisms: - In vacuum near threshold a partly non-reversible cyclic slip mechanism results in crack propagation. For higher loads after this cyclic slip mechanism the crack tip begins to blunt and after each fatigue cycle a fatigue striation is left on the crack surface - In air and nitrogen, near threshold, the crack growth increment is given by the oxide film thickness build-up after each half cycle. For higher loads the crack tip is blunted and fatigue striations occur o the crack surface - The main outcome of these experiments was to proof the hypothesis that the crack growth increment near threshold in air and nitrogen is the oxide film thickness. Corrosive liquids would result in further acceleration of the processes
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How to avoid Corrosion Fatigue

Same measures than for Stress Corrosion Cracking Further indicated is: Decrease of the stress amplitude under a critical value (look at the Whlers curve parameters) Try to have a smooth surface (avoid notches or localized corrosion attack) in the areas where stress is expected Try to avoid resonance frequencies of the structure (design consideration) Improve the passivation of the surface. Brittle coating do not help, organic coating is better in this case 33