Hydrogen Embrittlement Resistance and

Diffusible Hydrogen Desorption Behavior of

Multi-pass FCA Weld Metal
ECO Materials & Processing Laboratory
School of Materials Science and Engineering
Pusan National University

Contents
I
Introduction
Conclusion IV
Experimental procedures II
Results & Discussion
III
- 1
st
year conclusion & discussion
- 2
nd
year conclusion & future plan
Issue
Offshore plant industry needs excellent performance of steel and
welding material.
High strength, Low temp. toughness, CTOD and Low hydrogen contents
As the improved weldability of steels, cold crack occurs in weld
metal more than HAZ. [6,7]
Research Objective
Objectives
Evaluation on hydrogen embrittlement resistance of multipass weld metal.
Analysis on hydrogen trapping site by thermal desorption spectrometry.
Fig. Typical hydrogen trapping sites
Grain boundary Precipitates Dislocation
H Degradation of Mechanical Property
There are many embrittling effects of hydrogen on steels: the ultimate
strength may be reduced, ductility and reduction of area may be decreased,
and crack growth may be significantly accelerated. - STEES, G. Krauss [1].
HDF of TWIP Steel for automotive [2],[3]
Cold Crack in Steel Welds [5] Hydrogen-induced toughness drop [6]
HIC and SSCC in Linepipe Steel [4]
Theories of Hydrogen Embrittlement
Numerous HE mechanisms have been proposed to explain
the effect of hydrogen on the mechanical properties of
materials.

Decohesion theory
Decohesion theory states that dissolved hydrogen
migrates into a triaxially streesed region and embrittles
the lattice by lowering the cohesive strength between
metal atoms. [8]

Hydrogen
molecule
Defect
Internal pressure theory
The pressure of hydrogen in bubbles provides the stress
for the formation and propagation of a crack. [9]
Hydrogen atom
Dislocation
Hydrogen enhanced localized plasticity theory
Hydrogen enhancement of the dislocation mobility, which
allows dislocation to move at a lower applied stress.
Enhanced plasticity has been claimed to result in localized
softening which enhances plastic instability. [10]
STRESS
Diffusible Hydrgen
Microstructure
Etc.
Hydrogen Trapping Phenomena
Fig. Representative data for the apparent
diffusivity of hydrogen in iron and in
ferritic steels. [11]
Abnormality of hydrogen diffusion
F
r
e
e

E
n
e
r
g
y

E
s
E
B
E
aT
Trap site energy, G
T
Lattice site energy, G
L
Reversible (weak) trap
(Low activation energy)
Irreversible (strong) trap
(High activation energy)
Temperature ()
H
y
d
r
o
g
e
n

d
e
s
o
r
p
t
i
o
n

r
a
t
e


(
m
a
s
s

p
p
m
/
s
)

Hydrogen trapping
Activation energy for hydrogen trapping
* E
aT
: Trap activation energy
ECO Materials and Processing Laboratory
Contents
I
Introduction
Experimental procedures
Summary & Ongoing research IV
II
Results & Discussion
III
Y-groove test
200mm
150mm
80 60 60
Y-groove
weld
Anchor
weld
Anchor
weld
60
o
Gap : 20.5mm

50mm

Y-groove weld
50mm

Anchor weld
L1
L2
Measurement
: Stereoscopic microscope, Image analysis
Crack ratio(%) =
% 100
1
2

L
L
Welding method
Specimen Preparation
Multipass weld metal for TDS, CLT
Base metal
Welding
material
Welding
process
Welding
position
Shielding gas Gas flow rate
EH 36 30t FCW-1/2/3 FCAW Flat CO
2
100% 20 ~ 25 l/min
Voltage Current Heat input Welding speed
Number of
pass
Interpass temp.
27V 240A 7kJ/cm 50cm/min 36 150
45 2
2

45 2
20 mm
10 mm
10 mm
6 mm
M10
Welding condition
FCW-1/3 : AWS E91T1-Ni2C (AWS A5. 29), 1.2mm (diameter)
FCW-2 : AWS E81T1-K2C (AWS A5. 29), 1.2mm (diameter)
Experimental Setup for HE
Elements Amount
H
2
O 200 ml
NaCl 6 g
NH
4
SCN 0.6 g
Hydrogen pre-charging
Constant current density
- TDS : 1, 10, 50 A/m
2
, 24h
- CLT : 50A/m
2
, 24h
Constant loading test
Notch tensile specimen
Electrochemical plating of Cd (30~50um
thickness) to prevent hydrogen emission
Various stress ratio proportional to notch
tensile strength
Thermal desorption spectrometry
Carrier gas Heating rate
- 200, 300 /h
PDD detector
Column
[ TDS @ PNU ]
Detecting released hydrogen with
increasing temperature
Calculation of activation energy
Prediction of trapping site
ECO Materials and Processing Laboratory
Contents
I
Introduction
Experimental procedures
Results and Discussion
Conclusion
III
IV
II
Welding Materials
1
st
year
- Chemical Composition
- Mechanical Properties
No
Chemical Composition (wt.%)

C Si Mn Ni Cr Mo Ti Al V
B
[ppm]
Cu Nb
DW-62L 0.075 0.27 1.32 2.49 0.03 0.012 0.039 0.001 0.008 32 0.021 0.009 KOBE
SC-81K2 0.053 0.29 1.19 1.59 0.03 0.004 0.030 0.011 0.023 24 0.021 0.016
SC-91LT-1 0.062 0.22 1.19 2.06 0.03 0.003 0.041 0.019 0.002 44 0.016 0.008

SC-91LT-2 0.059 0.42 1.44 2.55 0.03 0.003 0.058 0.003 0.012 57 0.025 0.012
No
Mechanical Properties
YS [MPa] TS [MPa] El [%]
Impact test
Temp.
Avg.
Impact test
Temp.
Avg.
DW-62L 602 655 26.4
-60
109 J
-80
80 J
SC-81K2 551 583 28.2 154 J 135 J
SC-91LT-1 632 644 24.4 75 J 59 J
SC-91LT-2 675 695 23.4 92 J 50 J
1
st
year
Ceq & Pcm
14 4 5 40 24 6
V Mo Cr Ni Si Mn
C Ceq
B
V Mo Cr Ni Cu Mn Si
C Pcm 5
10 15 20 60 20 20 30

No Ceq Pcm
DW-62L 0.378 0.212
SC-81K2 0.312 0.166
SC-91LT-1 0.328 0.188
SC-91LT-2 0.388 0.220
1
st
year
Measurement of Cold crack
No DW-62L SC-81K2 SC-91LT-1 SC-91LT-2
R.T
50
100
150
Crack Crack Crack Crack
Crack Crack
1
st
year
Microstructure
Weld Metal Microstructure(Not Preheated)
Acicular Ferrite, Upper Bainite, Granular Bainite, Martensite
DW-62L
( Ceq 0.378 / 387 Hv )
SC-81K2
( Ceq 0.312 / 357 Hv )
SC-91LT-1
( Ceq 0.328 / 379 Hv )
SC-91LT-2
( Ceq 0.388 / 388 Hv )
AF
20.7%
B, M
79.3%
AF
40.9%
B, M
59.1%
AF
28.6%
B, M
71.4%
AF
45.7%
B, M
56.3%
1
st
year
Analysis of Cold crack
No RT 50
DW62 45.4 % 24.9 %
SC81K2 45.1 % -
SC91LT-1 39.5 % -
SC91LT-2 48.1 % 41.7 %
Cold Crack Resistance
SC-91LT-1 > SC-81K2 > DW62L SC91LT-2
Cold Crack Ratio
1
st
year
Fractographs
No DW-62L SC-81K2 SC-91LT-1 SC-91LT-2
R.T
50 No Crack No Crack
Not Preheated : Intergranular Fracture
Hydrogen related fracture

Preheated 50 : Intergranular Fracture + Cleavage Fracture
Hydrogen emission and reduction of cooling rate occurred due to the preheating
Microstructure (DW-62L)
(a)
(b)
(a) As-deposited region : GBF , WF (5%) + AF (76%) + Bainite (19%)
2mm
(b) Coarse grain reheated region : Granular bainite, Bainitic ferrite
PAZ
Bainite (with parallel laths)
Granular
Bainite
AF
Bainite
Granular
Bainite
1
st
year
Microstructure (SC-81K2)
(a)
(b)
2mm
(a) As-deposited region : GBF , WF (18%) + AF (82%)
(b) Coarse grain reheated region : Granular bainite +Bainitic ferrite
AF
GBF
Bainitic ferrite
1
st
year
Microstructure (SC-91LT-1)
2mm
(a)
(b)
(a) As-deposited region : GBF , WF (7%) + AF (84%) + Bainite (9%)
(b) Coarse grain reheated region : Granular bainite +Bainitic ferrite
PAZ
GBF
AF
Bainite
Bainite
1
st
year
1
st
year
Thermal Desorption Spectrometry
The amount of released diffusible H : DW-62L > SC-91LT1 > SC- 81K2
Symbol Diffusible H contents
DW-62L 4.65 ppm
SC-81K2 0.95 ppm
SC-91LT-1 2.76 ppm
Heating rate : 200/h
Analysis time : 240min
Current density : 50A/m
2
0 200 400 600 800
0.0000
0.0005
0.0010
0.0015
0.0020
H
y
d
r
o
g
e
n

d
e
s
o
r
p
t
i
o
n

r
a
t
e
,

p
p
m
/
s
e
c
Temperature,
o
C
DW-62L
SC-81K2
SC-91LT-1
Constant Loading Test
Charging condition
- 50A/m
2
, 24h
No charged specimens didnt rupture in 0.9 notch tensile strength.
The fracture time for the H charged specimens
: SC-81K2 > SC-91LT-1 > DW-62L
SC-81K2 showed the highest HE resistance.
0.1 1 10 100
0.0
0.1
0.2
0.6
0.7
0.8
0.9
1.0
DW-62L
SC-81K2
SC-91LT1
S
t
r
e
s
s

r
a
t
i
o
Time-to-Failure (hour)
No charged
1
st
year
Fractographs (Tensile vs. CLT)
Notch tensile test (before H charging) : Dimple type fractographs
CLT (after H charging) : Intergranular + Quasi-cleavage type fractographs
No No Charging (notch tensile test) After Charging (constant loading test)
DW-62L
SC-91LT1
1
st
year
Welding Materials
-Chemical Composition
-Mechanical Properties
No
Chemical Composition (wt.%)

C Si Mn Ni Cr Mo Ti Al V B Cu Nb
SF-36E 0.050 0.30 1.41 1.36 0.027 0.0002
0.060
0
0.009
5
0.013
0
0.004
0
0.190
6
0.013
5
Nittetsu
ARS 12C 0.078 0.38 1.30 0.007 0.038 0.0012
0.043
4
0.004
5
0.019
7
0.005
6
0.056
0
0.012
4
Fileur
SC-91LT
(Fold)
0.050 0.29 1.33 2.77 0.039 0.00057
0.050
3
0.011
6
0.006
1
0.004
5
0.024
4
0.007
9

SL-91LT-
1
(seamless)
0.048 0.43 1.62 2.667 0.028 0.004
0.060
4
0.005
6
0.009
7
0.005
3
0.271
1
0.010
4
SL-91LT-
2
(Seamless)
0.045 0.36 1.28 2.856 0.027 0.003
0.042
0
0.005
0
0.005
0
0.004
2
0.250
0
0.007
0
No
Mechanical Properties
YS [MPa] TS [MPa] El [%]
Impact test
Temp.
Avg.
Impact test
Temp.
Avg.
SF-36E 681 700 21.6
-50
98
-60
91
ARS 12C 607 664 22 104 67
SC-91LT (Fold) 586 632 24 115 102
SL-91LT-1
(Seamless)
602 658 23.6 66
SL-91LT-2
(Seamless)
604 635 26.6 75
2
nd
year
Ceq & Pcm
14 4 5 40 24 6
V Mo Cr Ni Si Mn
C Ceq
B
V Mo Cr Ni Cu Mn Si
C Pcm 5
10 15 20 60 20 20 30

No Ceq (IIW) Pcm
SF-36E 0..406 0.185
ARS 12C 0.404 0.196
SC-91LT (Fold) 0.469 0.199
SC-91LT-1 (Seamless) 0.522 0.230
SC-91LT-2 (Seamless) 0.472 0.204
2
nd
year
2
nd
year
No SF-36E ARS-12C SC-91LT SL-91LT-1 SL-91LT-2
R.T
50
100
Measurement of Cold crack
CRACK CRACK
CRACK
CRACK CRACK CRACK
CRACK
CRACK CRACK CRACK
CRACK
2
st
year
Microstructure
Weld Metal Microstructure(Not Preheated)
Acicular Ferrite, Upper Bainite, Granular Bainite, Martensite
SF-36E
( Ceq 0.406 / 387 Hv )
ARS-12C
( Ceq 0.404 / 363 Hv )
SC-91LT
( Ceq 0.469 / 334Hv )
SL-91LT-1
( Ceq 0.522 / 354 Hv )
SL-91LT-2
( Ceq 0.472 / 350 Hv )
AF
33.
5%
B,
M
66.5
%
AF
39.
6%
B,
M
60.4
%
AF
48.
7%
B,
M
51.3
%
AF
42.
3%
B,
M
58.7
%
AF
54.
7%
B,
M
45.3
%
SF-36E ARS 12C SC-91LT (F) SC-91LT-1 (S) SC-91LT-2 (S)
0
10
20
30
40
50
60
70
P
h
a
s
e

f
r
a
c
t
i
o
n
,

%
AF
B, M
2
nd
year
Cold Crack Resistance
ARS-12C > SL-91LT SF-36E > SL-91LT-1 SL-91LT-2
Cold Crack Ratio

No RT 50 100
SF-36E 42.5% 30.7% -
ARS-12C 32.9% - -
SC-91LT 41.9% 31.9% -
SL-91LT-1 46.3% 39.6% 27.5%
SL-91LT-2 45.1% 38.7% 12.5%
Analysis of Cold crack
No Contents
2014
Period
(Month)
1 2 3 4 5 6 7 8 9 10 11 12
1 TDS (2
nd
year sample) (2.5)
2 CLT (2
nd
year sample) (2.5)
3 Microstructure [ 2
nd
year sample] [2.5]
4 3
rd
year sample production (1)
5 Y-groove Test (3)
6 TDS (3
rd
year sample) (3)
7 CLT (3
rd
year sample) (3)
8 Interim Report
Future Plan
ECO Materials and Processing Laboratory
Contents
I
Introduction
Experimental procedures
Results & Discussion
Conclusion
III
IV
II
Weld metal consists of widmanstatten ferrite, acicular ferrite, grainboundry ferrite, bainite and
martensite. In different composition weld metal, weld metal which has higher Pcm and Ceq
contains more hardness phase.


Conclusion
Because diffusible Hydrogen is major factor in cold crack, we experiment with TDS. In no
hydrogen charging specimen, minute amount of diffusible hydrogen was released. A case o f
charging, specimen including amount of hardness phase released more diffusible hydrogen.
There is no clear difference between the non diffusible hydrogen.
In CLT test, specimen which has lower Pcm and Ceq has more hydrogen embrittlement
resistance. Because specimen which has higher Pcm and Ceq has high bainite and martensite
fraction


In Y-groove test, specimen which has more ferrite phase fraction has higher hydrogen
embrittlement resistance.




Reference
[1] G. Krauss : Steels-Heat Treatment and Processing Principles (1990 Edition), ASM International, 1990, 241-244
[2] Youngwoo Kim, Namhyun Kang, Youngdo Park, Ildong Choi, Gyosung Kim, Sungkyu Kim and Kyungmox Cho :
Effects of the Strain Induced Martensite Transformation on the Delayed Fracture for Al-added TWIP Steel, Korean J.
Met. Mater., 46 (2008) 780-787
[3] Young Soo Chun, Ji Soo Kim, Kyung-Tae Park, Young-Kook Lee and Chong Soo Lee : Role of epsilon martensite in
tensile properties and hydrogen degradation of high-Mn steels, Materials Science and Engineering A, 533 (2012), 87-95
[4] B. Beidokhti, A. Dolati, and A.H. Koukabi : Effects of alloying elements and microstructure on the susceptibility of
the welded HSLA steel to hydrogen-induced cracking and sulfide stress cracking, Materials Science and Engineering A,
507 (2009), 167-173
[5] Hee Jin Kim and Bong Young Kang : Evaluation Methods for Cold Cracking Susceptibility of Deposited Metal,
Journal of KWJS, 20-4 (2002), 429-436
[6] Jung-A Lee, Dong-Hyun Lee, Moo-Young Seok, Un Bong Baek, Yun-Hee Lee, Seung Hoon Hahm and Jae-il Jang :
Hydrogen-induced toughness drop in weld coarse-grained heat-affected zones of linepipe steel, Materials
Characterization, 82 (2013), 17-22
[7] Hee Jin Kim and Bong Young Kang : Development of Welding Consumable for Controlling the Cold Cracking in
Steel Deposited Metal, Journal of KWJS, 20-3 (2002), 3-8
[8] A.R. Troiano : The Role of Hydrogen and Other Interstitials on the Mechanical Behavior of Metals, Transactions of
the ASM, 52 (1960), 151-177
[9] A.S. Tetelman and W. D. Robertson : The mechanism of Hydrogen Embrittlement observed in iron-silicon single
crystals, Trans. TMS-AIME, 224 (1962), 775-783
[10] C.D. Beachem : A New Model for Hydrogen-Assisted Cracking (Hydrogen Embrittlement), Metallurgical
Transactions, 3 (1972) 441-455
[11] Ji Soo Kim, You Hwan Lee, Duklak Lee and Chong Soo Lee : Effect of Intergranular Ferrite on the Hydrogen
Delayed Fracture Resistance of High Strength Boron-added Steel, Korean J. Met. Mater., 45 (2007) 506-513


Reference
[12] Kyoung Ho So, Ji Soo KIM, Young Soo CHUN, Kyung-Tae PARK, Young-Kook LEE and Chong Soo
LEE :Hydrogen Delayed Fracture Properties and Internal Hydrogen Behavior of a Fe-18Mn-1.5Al-0.6C TWIP Steel,
ISIJ Int., 49 (2009) 1952-1959
[13] Koichi Takasawa, Ryo Ikeda, Noboru Ishikawa and Ryoji Ishigaki : Effects of grain size and dislocation density on
the susceptibility to high-pressure hydrogen environment embrittlement of high-strength low-alloy steels, International
Journal of Hydrogen Energy, 37 (2012) 2669-2675
[14] F. Watkinson : Hydrogen cracking in high strength weld metals, Welding Journal, 58-9 (1969) 417-424
[15] Hee Jae Kang, Tae Woo Lee, Byung Hyun Yoon, Seo Jeong Park, Woong Seong Chang, Kyun Mox Cho and
Namhyun Kang : Microstructural Effects on Hydrogen Delayed Fracture of 600MPa and 800MPa grade Deposited Weld
Metal, Korean J. Met. Mater., 50 (2012) 52-58
[16] H.E. Kissinger : Reaction Kinetics in Differential Thermal Analysis, Analytical Chemistry, 29 (1957) 1702-1706
[17] W.Y. Choo and J.Y. Lee : Thermal Analysis of Trapped Hydrogen in Pure Iron, Metallurgical Transactions A, 13A
(1982) 135-140
[18] J.Y. Lee, S.M. Lee, K. Y. Lee and J.L. Lee : A Study on the Interaction of Nonmetallic Inclusions with Hydrogen in
AISI 5160 Spring Steel, Korean J. Met. Mater., 22 (1984) 1120-1128
[19] F. Huang, J. Liu, Z.J. Deng, J.H. Cheng, Z.H. Lu and X.G. Li : Effect of microstructure and inclusions on hydrogen
induced cracking susceptibility and hydrogen trapping efficiency of X120 pipeline steel, Materials Science and
Engineering A, 527 (2010) 6997-7001
[20] J.S. Seo, H.J. Kim and H.S. Ryoo: Microstructural parameter controlling weld metal cold cracking, Journal of
Achievements in Materials and Manufacturing Engineering, 27 (2008) 199-202
[21] P.H.M. HART : Resistance to Hydrogen Cracking in Steel Weld Metals, Welding Research Supplement, (1986) 14-
22
[22] Gyu Tae Park, Sung Ung Koh, Hwang Gyo Jung, Kyoo Young Kim : Effect of microstructure on hydrogen trapping
efficiency and hydrogen induced cracking of linepipe steel, Corrosion Science, 50 (2008) 1865-1871
[23] M.A. Arafin and J.A. Szpunar : Effect of bainitic microstructure on the susceptibility of pipeline steels to hydrogen
induced cracking, Materials Science and Engineering A, 528 (2011) 4927-4940
THANK
Thermal Analysis
2009
2011
normal interstitial site energy level trapping site
energy level .
Fig. Model for trapping site. En : Diffusion
activation energy of hydrogen in normal lattice.
E
s
: saddle point energy around the trapping site.
E
b
: Interaction energy between trapping site and
hydrogen. E
a
: Trap activation energy (E
s
+ E
b
).
A : Trapping site. B : Normal lattice site.
simple reaction .
H
trap trap
+ H (in lattice)
trapping site reaction thermally activated process,
X
T
: Trapping site
(1-X
T
) : Trapping site
Exp(-E
aT
/RT) : EaT
A
c

Thermal Analysis
2009
2011
, reaction rate

trapping site reaction rate .

heating rate ,




peak temperature ,

2
=

Heating rate peak temperature ,
hydrogen trap reaction trap activation energy .

= 0


Tc, highest peak temperature
Different heating rates,
Trap activation energy, E
aT
Thermal Analysis
2009
2011
trapping site ,
.

.

.

trapping site trapping
site trapping .


Tc, highest peak temperature
Different heating rates,
Trap activation energy, E
aT
Hydrogen Embrittlement in Steel Welds
TMCP (Thermo-mechanical controlled process)
. Ceq . . [9],
[10]

. [10], [11], [12]


. [13]
. [14]
Fig. Variation of carbon equivalent with the
strength level of shiphull structural steel.