Corrosion at Microscale

Dr. Yaiza Gonzalez-Garcia

Assistant Professor
Corrosion Technology and Electrochemistry
Materials Science and Engineering
3mE-Faculty

1st training school – mcBEEs network, Delft 15-20 July 2018

Lecture
Corrosion at Microscale

• “Bulk” materials

• Micro- & nano-dimensional

components
Lecture
Corrosion at Microscale

• “Bulk” materials
 (in aqueous or wet conditions)
Degradation of metal due to electrochemical reaction with the
environment

anode M ® M2++2e-
Double layer

-
H
2O
cathode 1/2O2 + H20+2e-

2e- M(OH)2

by D. Koleva
SOLUTION

M - Anode (for M oxidation or anodic reaction)

anode M2++2e-
- Cathode (for H+ or O2 reduction or cathodic reaction)
- Electrolyte (ion conduction)
- Electrical contact between anode and cathode
(e- conduction)
Corrosion Forms

Uniform Corrosion

Localised Corrosion
 Localised corrosion

Local solution chemistry: ion types, concentration,

Local
pH, temperature, convection, ... electrochemical
activity

Solution

Metal

Metal microstructure: surface and

bulk properties
 Localised corrosion
Local solution chemistry: ion types, concentration,
pH, temperature, convection, ...

The interaction between a given environment plays a central role in

electrochemical processes.

Thermodynamic Stirring of the solution

 Localised corrosion
Local solution chemistry: ion types, concentration,
pH, temperature, convection, ...

The interaction between a given environment plays a central role in

electrochemical processes.
 Localised corrosion
Local solution chemistry: ion types, concentration,
pH, temperature, convection, ...

The interaction between a given environment plays a central role in

electrochemical processes.

Dynamic local environment

 Localised corrosion
Local solution chemistry: ion types, concentration,
pH, temperature, convection, ...

The interaction between a given environment plays a central role in

electrochemical processes.

Dynamic local environment

* Image martensitic steel after 20hours immersion in 3.5% NaCl solution by Xiaolin Li (TU Delft)
 Localised corrosion
Local solution chemistry: ion types, concentration,
pH, temperature, convection, ...

The interaction between a given environment plays a central role in

electrochemical processes.

Dynamic local environment

Atmospheric corrosion
 Localised corrosion

Local solution chemistry: ion types, concentration,

pH, temperature, convection, ...

Solution

Metal

Metal microstructure: surface and

bulk properties
- oxide integrity
- oxide thickness
- oxide electronic properties - grain size
- intermetallic (IM) types - grain boundary segregation
- IM composition
- IM distribution
 Microstructure of the metal influences
• mechanical strength and wear resistance
• corrosion resistance

nanoscale microscale mesoscale

Phases
Precipitates

Lattice structure Cracks

Texture

1st training school – mcBEEs network, Delft 15-20 July 2018

 Grain Size

Grain refinement improves mechanical properties such as

strength, wear, and ductility, by way of Hall-Petch-type
relations without modification of the base alloy chemistry

• There is little consensus as to the exact relationship between

grain size and corrosion depending on the alloy system

• In many cases within the same alloy system, contradictory

conclusions have been published claiming that decreased
grain size can variably increase and decrease corrosion
resistance

CORROSION—Vol. 66, No. 7 (2010)

1st training school – mcBEEs network, Delft 15-20 July 2018
 Grain Size

Grain refinement improves mechanical properties such as

strength, wear, and ductility, by way of Hall-Petch-type
relations without modification of the base alloy chemistry

where d is the strengthening coefficient and both k and x are

material specific.

where σy is the yield stress, σo is a materials constant for the starting

stress for dislocation movement (or the resistance of the lattice to
dislocation motion), ky is the strengthening coefficient (a constant
specific to each material), and d is the average grain diameter.

The smaller the grain size, the smaller the repulsion stress felt by a grain
boundary dislocation and the higher the applied stress needed to propagate
dislocations through the material.
1st training school – mcBEEs network, Delft 15-20 July 2018
CORROSION—Vol. 66, No. 7 (2010)
1st training school – mcBEEs network, Delft 15-20 July 2018
 Grain Size Influence

1st training school – mcBEEs network, Delft 15-20 July 2018

From review by K.D Ralston and N. Birbilis, Corrosion 22 (2010) 075005-1
 Grain Size

CORROSION—Vol. 66, No. 7 (2010) *curves are not applicable to Mg or Ni

1st training school – mcBEEs network, Delft 15-20 July 2018
19
 Grain Size

• Limitation to study the effects of grain size on corrosion

resistance is the difficulty in isolating grain size effects from
other microstructural changes (that are caused by
thermomechanical processing used to achieve variation in
grain size

Difficulty in insulating the effects in corrosion of

one microstructural feature from the others

CORROSION—Vol. 66, No. 7 (2010)

1st training school – mcBEEs network, Delft 15-20 July 2018
 Intermetallics (IMs)

1st training school – mcBEEs network, Delft 15-20 July 2018

AA2024 Aluminium alloy
AA2024 alloy is an aluminium alloy with copper as the primary alloying
element
AA2024-Tx is one of the most common high-strength aluminium alloys used
in the aerospace industry.

Component wt%
Aluminium 92.99
Cu 4.45
Mg 1.57
Mn 0.56
Fe 0.17
Zn 0.16
Si 0.06
Others 0.04
 AA2024 Aluminium alloy: Microstructure

• AA2024 has one of the most complicated microstructures of all the Al

alloys

• It has one of the highest levels of added alloying metals, as well as

impurities such as Fe and Si

• A key aspect of the microstructure is the intermetallic particles (IMs).

A.E. Hughes et al.: Microstructure and corrosion of AA2024-T3,

Corros Rev 2015; 33(1-2): 1–30
 AA2024 Aluminium alloy: Microstructure
Family of Intermetallic (IMs)
Microstructure

Electron probe microanalysis (EPMA) mapping combined

with EDS analysis.

A. E. Hughes et al., Surf. Interface Anal. 2010, 42, 334–338

Corrosion of AA2024 alloy
Interest in corrosion of AA2024-T3 stems from a need to understand the
influence of corrosion on mechanical properties

Strong influence of the microstructure in the corrosion performance

Before

After
 Passivity of AA2024 alloy
The presence of the IMs forms a heterogeneous structure, which makes difficult
the growth of the protective oxide layer formed in air or in aqueous solutions
on the alloy

Passive layer

S-phase Al3+
(Al3Fe)
(Al2CuMg)

Major IM (60%)

Intermetallics Al matrix
Corrosion of AA2024 alloy

Na+ Cl-
Cl-
Na+

Passive layer Cl-

Cl-
Cl- Cl- Cl-
Cl-
S-phase Al3+
(Al3Fe)
(Al2CuMg)

Major IM (60%)

Intermetallics Al matrix
 Corrosion of AA2024 alloy
Penetration Mechanism
Na+ Cl-
Cl-
Na+

Cl-
Cl-
Cl- Cl- Cl-
Cl-
Al3+
(Al3Fe)

%)

Intermetallics Al matrix

Film breaking mechanism Adsorption Mechanism

Corrosion of AA2024 alloy

Before

After

immersion in 1.5 M NaCl solution for 45 min

Corrosion of AA2024 alloy
 Corrosion of AA2024 alloy

Electrochemical properties

Synthetized macroscopic intermetallic compounds

(IMC’s)

Anodic IMs

Cathodic IMs

A.E. Hughes et al., Corrosion Science 52 (2010) 90–103

Corrosion of AA2024 alloy

Conceptual Model of Particle-Matrix Interaction

Al3+ Al3+

Cathodic Particle
e- e-
Matrix
dissolution M+
Matrix M+

e- Anode e-
Anodic Particle
Particle Al matrix
dissolution
Corrosion of AA2024 alloy
OCP (V vs. SCE)
Al3Fe -0.47
C Al2Cu -0.70
Al -0.76
Na+ Cl-
Cl-
Na+ A Al2CuMg -0.91
Al3Mg2 -1.15
Natural Al(OH)3
(porous)

S-phase Al3+
(Al3Fe)
(Al2CuMg)

Major IM (60%)

Intermetallics Al matrix
Al3+ + Cl- + H2O = |…| = Al(OH)2Cl + H+
(highly soluble and instable = no protective Al(OH)3 )
Corrosion of AA2024 alloy
OCP (V vs. SCE)
Al3Fe -0.47
Al2Cu -0.70
Al -0.76
Na+ Cl-
Cl- Al2CuMg -0.91
Changes from Na+
anodic S-phase to Al3Mg2 -1.15
cathodic Al2Cu
Mg2+ Al3+
O2 OH- O2 OH-

S-phase (Al3Fe)
(Al2CuMg) e-
e-

Intermetallics Al matrix
Corrosion of AA2024 alloy
OCP (V vs. SCE)
Al3Fe -0.47
Al2Cu -0.70
Al -0.76
Na+ Cl-
Cl- Al2CuMg -0.91
Na+
IMs are lost Al3Mg2 -1.15

Al3+ Al3+
O2 OH- O2 OH-

Cathodic Al2Cu (Al3Fe)

e- e-

IMs (cathodes) Al matrix (anode)

Corrosion of AA2024 alloy
Behaviour IMs AlCuMg
Corrosion of AA2024 alloy
Behaviour IMs AlCuMg
Corrosion of AA2024 alloy
OCP (V vs. SCE)
Al3Fe -0.47
Al2Cu -0.70
Al -0.76
Na+ Cl-
Cl- Al2CuMg -0.91
Na+
IMs are lost Al3Mg2 -1.15

Al3+ Al3+
O2 OH- O2 OH-

Cathodic Al2Cu (Al3Fe)

e- e-

IMs (cathodes) Al matrix (anode)

Corrosion of AA2024 alloy

Na+ Cl-
Cl-
Na+

Al3+
O2 OH-
Propagation mechanism

e-
e-

IMs (cathodes) Al matrix (anode)

Autocatalytic reaction inside of the pit

Al3+ + 3H2O + 3Cl- à Al(OH)3 + 3HCl
 AA2024 Aluminium alloy: Microstructure

A. E. Hughes et al., Surf. Interface Anal. 2010, 42, 334–338

 Inclusion
Presence of MnS inclusions in stainless steel

E particle ~ -0.4V

E bulk ~ -0.25V

MnS inclusion on a SS 304 plate

T. Suter, H. Bohni / Electrochimica Acta 47 (2001) 191–199

1st training school – mcBEEs network, Delft 15-20 July 2018
 MnS inclusion on a SS 304 plate

Corrosion behavior of different zones of the single MnS inclusion on a SS 304 plate (0.026% S) in 1 M NaCl
1st training school – mcBEEs network, Delft 15-20 July 2018
T. Suter, H. Bohni / Electrochimica Acta 47 (2001) 191–199
 “Bulk” Material. Challenges
Insulate the effects in corrosion of one microstructural
feature from the others

Electrochemical characterization:
In-situ measurements and high-resolution

Systematic study of the different microstructural

features affecting corrosion

1st training school – mcBEEs network, Delft 15-20 July 2018

 Corrosion at Microscale

• “Bulk” materials

• Micro- & nano-dimensional

components
 Corrosion is the main restriction on many
nanotechnology applications.

Demand for knowledge about

corrosion is growing, with the
increasing use of advanced
materials in medical devices,
biosensors, fuel cells, batteries,
solar panels and microelectronics.

* https://www.dreamstime.com/

X. Li et al., Nature 527 (2015) 441-442

• Corrosion processes in nanoparticles, nanowires or
other nano- and micro-engines are scarcely studied

• Studies are limited to investigate the degradation and

the corrosion products using surface analysis or
microscopy techniques
• Corrosion phenomena occurring in micro- and nano-dimensional components can
follow a completely different path than in their bulk conditions.

• Defects of nanometric dimensions become more important

• Integration of several materials being in physical or electrical contact might lead to galvanic
coupling. Causing degradation of the less noble material or its complete dissolution due to
its small dimensions.

How the shape of a small-scale structure influences the corrosion?

• Certain geometries can critically favor corrosion processes such as

crevice corrosion and pitting

• Other aspect is the study of specific defects in protective thin layers 1 μm

considered harmless in protected bulky pieces, but potentially
threatening in micro- and nanoparts
Wirebonding in microelectronic packaging

• Replacement of gold wirebonding for more

cost efficient materials. Copper is suitable
alternative
Generic example
• Copper ball bonds susceptible to moisture and
corrosion.
• More susceptible than gold

Failure analysis and Mechanism of Cu-ball bonds

Copper ball
• Highly accelerated temperature/humidity stress bond
test (HAST) Al bond pad
85% RH, 130oC, 3.6V
• Surface analysis

*Gan et al. , Effects of Wire Type and Mold Compound on Wearout Reliability of Semiconductor Flash Fineline BGA Package
Failure analysis and Mechanism of Cu-ball bonds

• Microcracking along the Cu-Al

interfaces
• Crack initiates from the edge of
Cu ball bonds
• Propagates toward the center
of the ball

*Gan et al. , Effects of Wire Type and Mold Compound on Wearout Reliability of Semiconductor Flash Fineline BGA Package
Failure analysis and Mechanism of Cu-ball bonds

Proposed mechanism • Failure most probably attributed to Cl-

Ionic Cl- is usually found at the
corroded ball bond.
• Cl attacks the edge of Cu ball bond
region
• Hydrolysis of IMC and AlCl3 (an
intermediate product) in a moist
environment forms Aluminum (III)
oxide which is a resistive layer.

• Cracking of the Al2O3 interface of Cu

to the Cu IMC might be due to out
gassing of H2 during hydrolysis

• Cracking usually starts at the Cu ball

bond periphery and will propagate
towards center of Cu ball bond
*Gan et al. , Effects of Wire Type and Mold Compound on Wearout Reliability of Semiconductor Flash Fineline BGA Package
Micro- & nano-components. Challenges

3D- geometry of the components

Complexity of the microstructures

Limited access to electrochemical measurements

Environment conditions. Atmospheric conditions & thin

film electrolyte

1st training school – mcBEEs network, Delft 15-20 July 2018

 Corrosion at Microscale

• “Bulk” materials

• Micro- & nano-dimensional

components
 Scientific challenges
Miniaturization of corrosion studies...

Microcapillary flow cell

54
 Scientific challenges
Miniaturization of sensing probes...

I. Heller, J. Kong, H. A. Heering, K. Williams, S. Lemay, C. Dekker

Individual single-walled carbon nanotubes as nanoelectrodes for electrochemistry
NanoLetters 5, 137 (2005)
I. Heller, J. Kong, K. A. Williams, C. Dekker, S.G. Lemay
Electrochemistry at Single-Walled Carbon Nanotubes: The Role of Band Structure and Quantum Capacitance
JACS 128, 7353 -7359, 2006.

55
 Modeling
Electrochemistry

Materials mCBEEs
Science

Technology
Engineerings needle
supporting
SECM-FM 7p SKP-FM probe

Industry
fiber
optical fiber
Uext
(φ20µm)
Electron-transfer Red Ox Volta-poten0al
kine0c
ΔΨ
e- oxide layer

Phase Phase
drop solution

Matrix/bulk material
y.gonzalezgarcia@tudelft.nl