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Application of GDOES to Study of Corrosion Protective Coatings
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Ruth Bingham, George Thompson, Peter Skeldon.
The University of Manchester
GD day 16th September 2016
Contents
• Background• MULTIPROTECT• Specimens
• Experimental
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• Experimental• Glow discharge optical emission
spectroscopy (GDOES)• Artificial cells
• Results and discussion• Summary and conclusions, further work
Project backgroundMULTIPROTECT:• An integrated project of the 6th framework
programme of the European Commission.• A collaboration between 31 academic and
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• A collaboration between 31 academic and industrial researchers from 13 countries.
• Aim: to provide novel, heavy-metal free, multifunctional, economical and environmentally friendly corrosion protecting surface treatments based on nanocomposite materials.
http://www.multiprotect.org/
Specimens: AA2024 T3
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• EPOXY-Al sol-gel coatings (INM)• Non-inhibited• Inhibited: BZT or BZT in AluOx;
• Methacryloxy-based sol-gel coatings (EADS)• Methacryloxy-based sol-gel coatings (EADS)• Non-inhibited• SAPP-inhibitor in sol-gel,• Inhibitors in primer: BZT, MBT, MBI,
SrCrO4.
Experimental: RF-GDOES
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• The sample is sputtered by Ar ions.• Neutral species
Arvacuum
window
λ
• Neutral species are accelerated in the plasma.• Light is emitted by the atoms when excited by collisions.
Vacuum
Cooling
Anode
SampleRF
Experimental: Artificial Cells
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• Cells consisted of coated specimens fixed in close proximity to the bare alloy:
• Cells were filled with 35 g l-1 NaCl
ge
l w
ith
BZ
Tg
el w
ith
BZ
T • Cells were filled with 35 g l NaCl solution for (a) 5 h and (b) 200 h.
• Subsequent GDOES analysis of the bare alloy from each cell.
• Noted characteristics of elemental profiles.S
ol-g
el w
ith
BZ
T
AA
20
24
-T3
So
l-g
el w
ith
BZ
T
AA
20
24
-T3
Experimental: Artificial Cells
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
^ Artificial cells during exposure ^ Artificial cells deconstructed
after exposureBare alloy specimens were then sputtered. Raw data was imported to Excel and combined to compare profiles of individual elements.
Results and Discussion
Part 1:Elemental depth profiles of the bare alloy from cells incorporating
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
alloy from cells incorporating uninhibited coatings
Surf. Interface Anal. 2015, 47, 1009 – 1014
60
80
Inte
nsi
ty
sol-gel + primer
High-Inorganic sol-gel
Aluminium profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
In the presence of coated specimens from EADS
0
20
40
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty High-Inorganic sol-gel
sol-gel + Zr
control
referenceSurface roughness > reference.
Surface roughness ≤ reference.
60
80
100
Inte
nsi
ty
EPOXY-Al
Aluminium profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Surface roughness > control but < reference
0
20
40
60
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty
EPOXY-Al-AluOx
control
referenceSurface roughness ≥reference.
6
8In
ten
sity
sol-gel + primer
High-Inorganic sol-gel
sol-gel + Zr
Oxygen profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Sputtering times to achieve half-peak intensity:
1.15 s
1.15 s
1.06 s
Area under the curve indicates thickness of corroded or altered
0
2
4
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty
sol-gel + Zr
control
reference
1.06 s
1.04 s
1.24 s
corroded or altered layer
3
4
Inte
nsi
ty
EPOXY-Al
EPOXY-Al-AluOx
Oxygen profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
1.25 s
1.04 s
Sputtering times to achieve half-peak intensity:
0
1
2
0 1 2 3 4 5 6 7Sputtering time (s)
Inte
nsi
ty
control
reference
0.82 s
1.04 s
Copper profiles of bare alloy
8
10
12
Inte
nsi
ty
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Note double peak for control specimen
Retention of second peak
0
2
4
6
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty
sol-gel + primer high-inorganic sol-gel
sol-gel + Zr control
referenceLoss of second peak indicates de-alloying and re-distribution of Cu
8
10
12
14
Inte
nsi
ty
EPOXY-Al
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Copper profiles of bare alloyNote double peak for control specimen
Retention of second peak
0
2
4
6
8
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty
EPOXY-Al
EPOXY-Al-AluOx
control
reference
Loss of second peak indicates de-alloying and re-distribution of Cu
0.02
0.03
Inte
nsi
ty
EPOXY-Al
EPOXY-Al-AluOx
Chlorine profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Area under the curve indicates quantity of Cl sampled when sputtering through the corroded or altered
0
0.01
0 1 2 3 4 5 6 7
Sputtering time (s)
Inte
nsi
ty
control
reference
corroded or altered layers.
Results and Discussion
Part 2:Elemental depth profiles of the bare alloy from cells incorporating BZT-
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
alloy from cells incorporating BZT-inhibited coatings (INM)
Surf. Interface Anal. 2015, 47, 1098 – 1108
60
70
80
90
100
EPOXY-Al-BZT
Aluminium profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Surface roughness > control but < reference
0
10
20
30
40
50
60
0 1 2 3 4 5Sputtering time (s)
Inte
nsi
ty
EPOXY-Al-BZT
EPOXY-Al-BZT-AluOx
EPOXY-Al (uninhib.)
EPOXY-Al-AluOx (uninhib.)
control
reference
Surface roughness
≥ reference
2.5
3
3.5
4 EPOXY-Al-BZT
EPOXY-AL-BZT-AluOx
EPOXY-Al (uninhib.)
EPOXY-Al-AluOx (uninhib.)
1.16 s
1.18 s
1.25 s
1.08 s
Oxygen profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
0
0.5
1
1.5
2
2.5
0 1 2 3 4 5
Sputtering time (s)
Inte
nsi
ty
EPOXY-Al-AluOx (uninhib.)
control
reference
1.08 s
0.82 s
1.04 s
Values = Sputtering times to achieve half-peak intensity
8
10
12
14
Copper profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Note double peak for control specimen
Significant retention of second peak
Loss of second peak: de-alloying of Cu
0
2
4
6
8
0 1 2 3 4 5
Sputtering time (s)
Inte
nsi
ty
EPOXY-Al-BZT EPOXY-Al-BZT-AluOx
EPOXY-Al (uninhib.) EPOXY-Al-AluOx (uninhib.)
control reference
Loss of second peak: de-alloying of Cu
0.015
0.02
0.025EPOXY-Al-BZT
EPOXY-Al-BZT-AluOx
EPOXY-Al (uninhib.)
EPOXY-Al-AluOx (uninhib.)
Chlorine profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
Area under the curve indicates quantity of Cl
0
0.005
0.01
0.015
0 1 2 3 4 5
Sputtering time (s)
Inte
nsi
ty
EPOXY-Al-AluOx (uninhib.)
control
reference
0.03
0.035
0.04
0.045In
ten
sity
EPOXY-Al-BZT
EPOXY-Al-BZT-AluOx
EPOXY-Al (uninhib.)
EPOXY-Al-AluOx (uninhib.)
Nitrogen profiles of bare alloy
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
0
0.005
0.01
0.015
0.02
0.025
0 1 2 3 4 5
Sputtering time (s)
Inte
nsi
ty
reference
Area under the curve indicates quantity of N sampled. Result inconclusive.
Summary and conclusions
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
• Comparison of the intensity of corrosion of the bare alloy can be made by inspection of Al depth profiles.
• Comparison of thickness of corroded layers can be made by inspection of the O depth profiles.
• Assessment of extent of de-alloying and re-distribution of • Assessment of extent of de-alloying and re-distribution of Cu can be made by inspection of depth profiles.
• An inhibitory effect of the empty AluOx nanocontainers, due to chloride absorption, was inferred rom the Cl depth profiles.
• Presence of BZT inhibitor could not be confirmed by inspection of N depth profiles.
Additional Work
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
A third paper has been published detailing a study of depth profiles obtained by sputtering the bare alloy after corrosion in the presence of the inhibitor-doped specimens from EADS:inhibitor-doped specimens from EADS:
Surf. Interface Anal. 2016, 48, 341 – 352
Thank you...
MULTIPROTECT: The University of ManchesterMULTIPROTECT: The University of Manchester
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