Post on 21-Jun-2015
description
IntroductionThe Model
Application to real processesConclusion
Understanding hydrogen redistribution anddesigning a new hydrogen extraction method
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net)
dgaude Prime Innovation SLUIndependent Research in Physical Metallurgy and Engineering
3rd UK-China Steel Research ForumRutherford Appleton Laboratory (UK)
10-11 July 2014
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
1 Introduction
2 The Model
3 Application to real processesAnalysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
4 Conclusion
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Embrittlement prevention methods
At the design stage (material & componentengineering)
Extraction from liquid metal during refining(Vacuum, AOD, et c.)
Extraction from solid at high temperature (veryslow cooling & directional cooling:METAL2010, HSLA2011, Euromat2011, Steel &Hydrogen2014, et c. )
Extraction by treating after cooling (Bakingtreatment: METAL2014)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Embrittlement prevention methods
At the design stage (material & componentengineering)
Extraction from liquid metal during refining(Vacuum, AOD, et c.)
Extraction from solid at high temperature (veryslow cooling & directional cooling:METAL2010, HSLA2011, Euromat2011, Steel &Hydrogen2014, et c. )
Extraction by treating after cooling (Bakingtreatment: METAL2014)
Can we still do anything else to reduce the incidenceof hydrogen embrittlement in metals?
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
The Model
Let’s start at the beginning:Let’s try and understand the redistribution of
interstitial elements
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
The Model
Let’s start at the beginning:Let’s try and understand the redistribution of
interstitial elements
An interstitial diffusion model
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Interstitial diffusion: Hydrogen
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Thermal evolution and T gradients (Heat Equation)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Thermal evolution and T gradients (Heat Equation)
Phase transitions from Liquid to α BCC (Thermodynamic Model)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Thermal evolution and T gradients (Heat Equation)
Phase transitions from Liquid to α BCC (Thermodynamic Model)
Hydrogen diffusion as random walk, driven by chemical activationgradient
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Thermal evolution and T gradients (Heat Equation)
Phase transitions from Liquid to α BCC (Thermodynamic Model)
Hydrogen diffusion as random walk, driven by chemical activationgradient (... think of it as following a partial saturation gradient)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Diffusion
Characteristics of the model:(METAL2010-2014, HSLA2011, EUROMAT2011, Steel& Hydrogen2014, et c.)
Thermal evolution and T gradients (Heat Equation)
Phase transitions from Liquid to α BCC (Thermodynamic Model)
Hydrogen diffusion as random walk, driven by chemical activationgradient (... think of it as following a partial saturation gradient)
Interstitial solubility and saturation as function of temperature andmatrix phase or trap type and distribution
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Model: Trapping
Each trap type characterisedby its characteristic releaseenergy barrier
Interaction of each of thetrap sites with lattice
Exchange with atmosphereat free surfaces: localequilibrium across thesurface (Sievert’s law)
E
E t
d
������������������������������������
������������������������������������
Trap_1 Trap_i Trap_n.. ..
Atm
osp
her
e
Lattice
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Application to real processes
What can we do with this model? (Very briefly)
Analysis of Casting (or any cooling process)
Development of new H extraction method
Analysis of Baking
... and much more!!
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Analysis of Casting (or any cooling process)
0
1
2
3
4
5
6
-12.5 -5 0 5 12.5 0
1
2H c
onte
nt /p
pm
Thickness /cm
Fast cooling Slow cooling
----
----
----
-cen
ter
piec
e---
----
-
0s 30s
150s 600s
1200s1700s
0h1h6h
24h42h 0
5
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45
-12.5 -5 0 5 12.5 0
5
10
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H p
artia
l sat
urat
ion
Thickness /cm
Fast cooling Slow cooling
----
----
---c
ente
r p
iece
----
----
---
0s 600s 900s
1200s1500s1700s
0h1h6h
24h42h
Steel: 25cm thick with 2ppm
Effect of cooling rate:
Fast cooling vs. Slow cooling
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Analysis of Casting (or any cooling process)
0
1
2
3
4
5
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-12.5 -5 0 5 12.5 0
1
2H c
onte
nt /p
pm
Thickness /cm
Fast cooling Slow cooling
----
----
----
-cen
ter
piec
e---
----
-
0s 30s
150s 600s
1200s1700s
0h1h6h
24h42h 0
5
10
15
20
25
30
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40
45
-12.5 -5 0 5 12.5 0
5
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15
H p
artia
l sat
urat
ion
Thickness /cm
Fast cooling Slow cooling
----
----
---c
ente
r p
iece
----
----
---
0s 600s 900s
1200s1500s1700s
0h1h6h
24h42h
Steel: 25cm thick with 2ppm
Effect of cooling rate:
Fast cooling vs. Slow cooling
Effect of thickness: (5-50cm)
Effect of FCC to BCC transformationtemperature:
Steel A: 700oC vs. Steel B: 450oC 1.5
2
2.5
3
3.5
4
4.5
5
5.5
6
5 10 20 30 40 50
Max
H c
onte
nt /p
pm
Thickness /cm
Alloy AAlloy BStart H
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
Development of a new hydrogen extraction method
“Understanding hydrogen redistribution during steel casting, and its effective extraction bythermally induced up-hill diffusion”
D. Gaude-Fugarolas, in: Journal of Iron and Steel Research International 18 supl.1.1 (2011)159–163.
Also at proceedings: High Strength Low Alloy (HSLA2011) International Conference, Beijing,China, 2011.
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
A severe temperature gradient forces hydrogen to flow towards the coreregion of a component, where it can reach severe supersaturation
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
A severe temperature gradient forces hydrogen to flow towards the coreregion of a component, where it can reach severe supersaturation
Actually, NO!!. The temperature gradient forces hydrogen to flowtowards higher temperature regions!!
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
A severe temperature gradient forces hydrogen to flow towards the coreregion of a component, where it can reach severe supersaturation
Actually, NO!!. The temperature gradient forces hydrogen to flowtowards higher temperature regions!!
Then, why don’t we try instead to redirect the hydrogen fluxtowards the surface?
(and eventually get rid of it)
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
Standard casting operation: Interstitialelement flux creates enriched regions atthe core of the piece
Pouring cup
Feeder
Casting
Riser
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
Standard casting operation: Interstitialelement flux creates enriched regions atthe core of the piece
Pouring cup
Feeder
Casting
Riser
Modified casting operation with a severethermal gradient towards the surfacebeing imposed, eliminating interstitials
Pouring cup
Feeder
Casting
Riser
Heating Element
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
0
1
2
3
4
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-12.5 -5 0 5 12.5
H c
onte
nt /p
pm
Thickness /cm
Hea
ted
Surf
ace
0s60s
300s1200s3600s8400s 0.01
0.1
1
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-12.5 -5 0 5 12.5
H p
artia
l sat
urat
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Thickness /cm
Hea
ted
Surf
ace
0s60s
300s1200s3600s7200s7600s8000s8400s
Steel: 25cm thick with 2ppm
Surface I: Fast cooling
Surface II: Kept at high temperature(i.e. 1500oC)
Temperature gradient maintained 2h
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Development of a new hydrogen extraction method
0
1
2
3
4
5
-12.5 -5 0 5 12.5
H c
onte
nt /p
pm
Thickness /cm
Hea
ted
Surf
ace
0s60s
300s1200s3600s8400s 0.01
0.1
1
10
-12.5 -5 0 5 12.5
H p
artia
l sat
urat
ion
Thickness /cm
Hea
ted
Surf
ace
0s60s
300s1200s3600s7200s7600s8000s8400s
Steel: 25cm thick with 2ppm
Surface I: Fast cooling
Surface II: Kept at high temperature(i.e. 1500oC)
Temperature gradient maintained 2h
Final H content 0.99ppm!!i.e 50% Reduction!!
Partial Saturation duringtreatment below 1.0 !!
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Analysis of Baking
Analysis of Baking
“On the effectiveness of baking as hydrogen embrittlement reduction treatment”D. Gaude-Fugarolas, in: Proceedings of METAL2014, 21-23 May, Brno, Czech Republic, 2014.
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Treatment after cooling: Baking
Storage of the metal components in over at low warmtemperature (typically 150-230 oC) for a long period,up to 24-48 hours.
The treatment aims to reduce internal stresses and toreduce hydrogen content.
If treatment is not performed immediately aftercasting and cooling, it might become ineffective.
Effectiveness of treatment varies.
Why does effectiveness of baking vary so much?
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Analysis of Baking
Hydrogen content: 1 ppm
Baking: 12h at 190oC or 300oC
Sites: Lattice, Dislocation, Grain boundary,Precipitate (& Desorption to atmosphere)
Steel A: Allotriomorphic Ferrite (725oC), largegrain, low dislocation density
Steel B: Bainitic/Martensitic Ferrite (450oC),small grain, high dislocation density
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Analysis of Baking
Hydrogen content: 1 ppm
Baking: 12h at 190oC or 300oC
Sites: Lattice, Dislocation, Grain boundary,Precipitate (& Desorption to atmosphere)
Steel A: Allotriomorphic Ferrite (725oC), largegrain, low dislocation density
Steel B: Bainitic/Martensitic Ferrite (450oC),small grain, high dislocation density
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(a0)
Steel ALATTICE
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(a0)
Steel ALATTICE
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(b0)
Steel B
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(b0)
Steel B
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(a1)
DISLOCATION
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(a1)
DISLOCATION
0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(b1)0.001
0.005
0.025
0.125
0.625
0 6 h 12 h
H c
onc
/ppm
Time /s
(b1)
0.0000
0.0001
0.0010
0.0100
0.1000
0 6 h 12 h
H c
onc
/ppm
Time /s
(a2)
Steel AGRAIN
0.0000
0.0001
0.0010
0.0100
0.1000
0 6 h 12 h
H c
onc
/ppm
Time /s
(a2)
Steel AGRAIN
0.0000
0.0001
0.0010
0.0100
0.1000
0 6 h 12 h
H c
onc
/ppm
Time /s
(b2)
Steel B
0.0000
0.0001
0.0010
0.0100
0.1000
0 6 h 12 h
H c
onc
/ppm
Time /s
(b2)
Steel B
0.35
0.40
0.45
0.50
0.55
0 6 h 12 h
H c
onc
/ppm
Time /s
(a3)
PRECIPITATE
0.35
0.40
0.45
0.50
0.55
0 6 h 12 h
H c
onc
/ppm
Time /s
(a3)
PRECIPITATE
0.35
0.40
0.45
0.50
0.55
0 6 h 12 h
H c
onc
/ppm
Time /s
(b3)0.35
0.40
0.45
0.50
0.55
0 6 h 12 h
H c
onc
/ppm
Time /s
(b3)
“On the effectiveness of baking as hydrogen embrittlement reduction treatment”D. Gaude-Fugarolas, in: Proceedings of METAL2014, 21-23 May, Brno, Czech Republic, 2014.
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Conclusions on Baking
The success of baking depends of the interaction of hydrogencontent, microstructure and trap distribution.
Some microstructures already saturate with low hydrogen contents,making baking useless.
In general, baking is only effective when the microstructure is farbelow saturation.
The baking temperature needs to be tailored to trap type and Hdistribution.
Some defects may even increase their H content during baking.
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Analysis of Casting (or any cooling process)Development of a new hydrogen extraction methodAnalysis of BakingFuture work
Future work
This is still work in progress...
Surface defects
Crack initiation
H absorption from atmosphere
To be presented at, may be, METAL2015, Brno, Czech Republic, May 2015.
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Conclusion
Conclusion
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Conclusion
To summarise...
Small amounts of hydrogen can endanger the integrity of criticalmetal components.
A physical model has been presented offering a correct description ofhydrogen redistribution during manufacturing operations.
Several methods exist to reduce hydrogen embrittlement in metal,but not always successful.
A new method has been presented to reduce hydrogen content usingof imposed temperature gradients.
(Patent filed in US, Europe, China, et c., Already awarded or inprocess, and open for licensing).
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction
IntroductionThe Model
Application to real processesConclusion
Thanks
Thank you for your attention!!
For more information, please visit (or email):primeinnovation.netdgaude@cantab.net
Daniel Gaude-Fugarolas, Ph.D, FCPS (dgaude@cantab.net) Understanding hydrogen redistribution and its extraction