1

HYDROGEN EFFECT ON MICROALLOYED STEEL MECHANICAL

PROPERTIES AFTER SEVERAL TEMPERING SCHEDULES

JULIO C.VILLALOBOS SERGIO A. SERNA

Postgraduate Student-CIICAp- CIICAp-UAEM, Cuernavaca,
UAEM, Cuernavaca, Morelos Morelos, Mexico.
Mexico.

BERNARDO CAMPILLO OSVALDO FLORES

FQ-UNAM /ICF-UNAM, ICF-UNAM, Cuernavaca, Morelos,
Cuernavaca, Morelos, Mexico. Mexico.

JESUS COLIN HUGO LOPEZ

FCQeI-UAEM, Cuernavaca, UWM CEAS, Milwaukee,
Morelos, Mexico Wisconsin, USA

ABSTRACT
The principal aim of this work is to present results about the hydrogen effects on
a high strength martensitic microalloyed steel plate developed for pipeline
construction. The microalloyed steel was subjected to three tempering schedules
that impairs their original mechanical properties with apparent no change in
their martensitic structure. Then was subjected to hydrogen charging and
evaluated by tensile test. The mechanical properties show lowering values in
both tensile and yield strength but toughness seems to be only slightly changed
possibly due to co-precipitation of complex nanoprecipitates during the
tempering schedules with dislocation-hydrogen interactions in the tensile tests.

INTRODUCTION
During the last three decades, significant progress in the development of high
strength and tough microalloyed steels. Important steps have been added to their
technology in their thermomechanical controlled processes (TMCP) such as:
improvement of rolling processes controlled rolling and cooling processes [1-3].
Also, due to the refining processes produce very clean steels with very low
contents of C, P, S and N. This induced the development of new alloy design
with microstructures comprising of either traditional ferrite-perlite or acicular
ferrite or lower temperature transformation products (bainite, martensite) [4, 5].
Through the advanced technology of TMCP microalloyed steel of very low
carbon content (0.04-0.1%), induced a complexity of microstructures, that
induce higher levels of strength (400-600 MPa) and acceptable toughness [6-7].
On the other hand, small amounts of carbide and nitride forming solutes as Nb,
Ti and V added influenced strongly the structure of the mechanical properties of
microalloyed steel [8]. Strain induced precipitation of carbonitrides during high
rolling temperature leads to modify the behavior of austenite microstructure and
at lower rolling temperature, the recrystallization behavior [9]. Thus, the grain
size of the resulting transformed microstructure is very small improving the
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mechanical properties [10]. Furthermore carbonitrides precipitate in the

transformed material, may lead to additional strengthening [11]. Accelerated
cooling after finishing rolling results in the more complex microstructure
(bainitic-martensitic) which causes further strengthening. However, tempering
treatments can be suitable to adjust the yield strength and toughness, or required
to relieve stresses after welding processes. The tempering effect on mechanical
properties will depend of treatment temperature and elapsed time, related to its
influence of variations in the nature of microstructural defects (dislocations,
carbides, grain boundaries, etc.) [12]. These changes are determinate mainly by
size, shape, composition and distribution of the precipitates formed during
TMCP and tempering processes.
On the other hand, hydrogen is a common element in the oil industry that can be
generated as a corrosion byproduct or by the application of welding with coated
electrodes in the fitting of pipelines or valves [13]. Variables such as:
microstructure, strength, dislocation-recovery and carbide nano-coprecipitation
can be very important for the hydrogen effects over the steel mechanical
properties. Hydrogen’s harmful effects over steels could be related to hydrogen
embrittlement (HE) and hydrogen-induced cracking (HIC) [14-16]. These
phenomena are associated with the amount of hydrogen absorbed by steel, and
its accumulation in the lattice and other defects; it raises cracking, blistering and
further failure of the material.
The HE of steels is well known and its dependence on their microstructure and
has been extensively investigated [17-19]. The HE effects are characterized by a
slight descend on the ductility up to a brittle fracture with a relatively low
applied stress, (<σy). Even, a few parts per million of hydrogen dissolved in
steel can cause cracking and loss of tensile ductility, particularly in high strength
steels [20-22].
The combined effects of the tempering processes and HE susceptibility over the
microstructures modify the mechanical properties of the steels, and depends of
hydrogen rate diffusion, trap sites density and the exposed stress level in the
presence of hydrogen; causing local concentration of segregated hydrogen in
tri-axial strain fields or on strain-induced defects [23].
The aim of this present work is to evaluate the hydrogen effect in high strength
steel mechanical properties by tensile test over different tempering schedule
processes. Also permeability tests were carry out in order to evaluate the
effective hydrogen diffusion.

EXPERIMENTAL PROCEDURE
The chemical composition of microalloyed steel is show in table 1. The steel
slab in as cast condition was reheated up to 1250°C and hot rolled above the
critical temperatures A1 and A3, and accelerated cooling process. As result of
this schedule the microstructure obtained was mainly a martensitic-bainitic
structure.
Samples were obtained for tensile test according to ASTM-E8 standard test [24].
The mechanical properties were evaluated in the as-rolled direction in the as-
cast and hydrogen charged (hc) samples (1 and 12 hours). The solution for hc
was 0.5M H2SO4 + 0.2gr As203 at 40 mA/cm². Several tempering treatments
were performed at 200, 400 and 600°C for 1, 3 y 10 min, and then hc at 12
hours; the mechanical properties were evaluated in these conditions.
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Table 1. Chemical composition of the microalloyed steel (wt %).

C Si Mn P S Cr Mo Ni Al Nb Ti
0.027 0.244 1.000 0.003 0.005 0.422 0.180 1.354 0.045 0.024 0.015

Also the permeability parameters were determined in 1mm thick samples

employing the Devanathan and Stachurski’s cell [25], according to the ASTM
G-148 standard test [26]. The samples were polarized to 300 mV from the rest
potential using a reference electrode of Ag/AgCl an oxidation solution of 0.1M
NaOH.

RESULTS AND DISCUSSION

The microstructure obtained of the microalloyed steel after the
thermomechanical process, is depicted in fig. 1. It is observed a composed
microstructure by martensite-bainite and acicular ferrite with randomize
orientation.

Fig. 1. Microstructure of microalloyed steel in as-hot rolled condition.

The evaluated tensile mechanical properties are shown in table 2. It can be

observed a considerable decrease at longer hc-time of the mechanical properties.
Also it is observed and increment of the embrittlement index, defined by [27]:

where and represent the area reduction without and with hydrogen
charged respectively.

Table 2. Mechanical properties of the microalloyed steel.

UTS σy Toughness
Condition %E %RA %
(MPa) (MPa) (MJ/cm³)
As-received 1111 959 12.49 60.95 105 ---------
1 hr- hc 951 815 11.72 60.68 97 0.44
12 hr- hc 814 752 9.21 49.92 59 18.09

These changes in the mechanical properties are attributed to hydrogen

embrittlement effect, at 12 hours of hc the samples showed “blistering”(see fig.
2), across of these features fracture path occur during the tensile test.
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Fig. 2. Blistering on fractured sample (marked with arrows).

This fracture mechanism did not appear at 1 hour of hc. It is well established
that this tendency is due to hydrogen absorption and diffusion during the
charging, where it can be trapped in the defects, and the molecular hydrogen is
formed [28].

The microalloyed steel in the as-received condition was tempered in a range of

temperatures (200-600°C) and from 1 to 300 min treatment time. Fig. 3 shows
the microhardness values obtained after the tempering treatment was performed.
From these results in general the microhardness tends to decrease as the
temperature increases. Specifically at shorter treatment times (1-3 min) the
reduction is less evident, and for greater times, above 30 min, this behavior is
more noticeable. Furthermore, it is clear that at 10 min this performance is not
attained, showing slight increment from 300-400°C then diminish at higher
temperatures. The former tendency may be due to a co-precipitation carbides
effect inside the martensite-bainite lathes which induces further strengthening
[29]; the latter may be influence by the decomposition of the remain unreacted
phases (austenite); lath space coarsening, and grow of present precipitates,
indicating the recovering process is arising during tempering [30].
440 1min
3min
420 10min
Microhardness (HV1)

30min
400 100min
380 300min

360
340
320
300
280
260
200 300 400 500 600
Tempering treatment (°C)

Fig. 3. Microhardness as a function of tempering treatment.

From the above results were selected three different temperatures where the
maximum and minimum microhardness values were obtained for hc tests.
Regarding, the samples tempered and hc condition showed at 200°C less
mechanical strength compared to the as-received condition, at 3 min, it is
observed a minimum values of mechanical properties; however, %E tend to
increase and toughness decreases. At longer times the behavior observed is to
increase UTS and YS and toughness (see fig. 4).
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1200 UTS 13 110

1100 YS Elongation
12 100
1000 Toughness

Toughness (MJ/cm³)
900 90
11
Stress (MPa)

800

Elongation (%)
80
700 10
600 70
500 9
60
400
8
300 50
200 7 40
100
0 6 30
1 min 3 min 10 min 1 min 3 min 10 min
Fig. 4. Results of mechanical properties obtained at 200°C-12 hrs hc. a) UTS,
YS, b) %E and toughness.

Fig. 5 shows the results obtained at 400°C, the mechanical strength is lower than
the as-received condition, with a slight tendency to increase it at longer
tempering times. However, their %E and toughness decreases.
1200 13 110
UTS Elongation
1100
YS 12 Toughness 100
1000
900 90

Toughness (MJ/cm³)
11
Stress (MPa)

800
Elongation (%)

80
700 10
600 70
500 9
60
400
8
300 50
200 7 40
100
0 6 30
1 min 3 min 10 min 300 min 1 min 3 min 10 min 300 min
Fig. 5. Results of mechanical properties obtained at 400°C-12 hrs hc. a) UTS,
YS, b) %E and toughness.

Furthermore, the results obtained at 600°C (see fig. 6), depicted the minimum
mechanical strength compared to the as-received condition. Although, the
tendency is to increase at 3 min of tempering treatment, also it increases its
toughness and %E. These variations could be due to the microstructural
evolution during the tempering processes (stages: recovery and migration of
dislocations, precipitates coarsening, etc.) [31]. These sites act as irreversible
hydrogen traps that keep the hydrogen trapped bring about embrittlement and
weakening of the matrix-precipitate interface [32]. In addition, hydrogen
stimulate the movement of dislocations that promotes plastic flow, resulting in
localized softening contributing to brittle fracture and the reduction of %E and
ductility [33]. In the present work this behavior is not shown, due to the several
complex mechanisms involved in tempering processes and the resultant
microstructures in the different stages, and its interaction with the hydrogen
diffusion.
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1200 13 110
1100 UTS Elongation
12 Toughness 100
1000 YS

Toughness (MJ/cm³)
900 90
11
Stress (MPa)

800

Elongation (%)
80
700 10
600 70
500 9
60
400
8
300 50
200 7 40
100
0 6 30
1 min 3 min 1 min 3 min
Fig. 6. Results of mechanical properties obtained at 600°C-12 hrs hc. a) UTS,
YS, b) %E and toughness.

In table 3 are shown the results obtained for the embrittlement index. In general,
the %EI varies inversely to %RA; without tempering treatment the minimum
value obtained was at 1 hr-hc, but increasing hc-time the %EI suddenly rises. In
the case of the tempered samples, the values in general fluctuate around the
value obtained in the maximum hc-time. However, samples at 400°C-10min hc-
condition showed the lower susceptibility to embrittlement. On the other hand,
samples at 400°C-300 min, 600°C-1 min hc-conditions, their %EI values
increase abruptly almost twice the fluctuate value, being more susceptible to
hydrogen embrittlement. This “anomalous” response between the %EI values
could be associated to different microstructural response to the tempering
treatment conditions. As mentioned regarding the mechanical properties
performance in the preceding section.

Table 3. Embrittlement index values obtained.

Condition %RA %EI
As- received 60.95 0
1 hr 60.68 0.4429
12 hr 49.92 18.096
200°C - 1 min 51.12 16.12
200°C - 3 min 50.25 17.55
200°C - 10 min 53.5 12.22
400°C - 1 min 50.61 16.96
400°C - 3 min 47.8 21.57
400°C - 10 min 59.6 2.21
400°C - 300 min 39.4 35.35
600°C - 1 min 27.32 55.17
600°C - 3 min 47.13 22.67

Table 4 shows the initial permeability test values been carried up to now. In
general the hydrogen flux values do not change, except for 400°C-10 min and
600°C-3min conditions. Regarding the effective diffusivity (Deff) their values do
not modify substantially and the apparent concentration (Capp) values, exhibit a
fluctuating behavior. This performance may indicate there is an agreement
already confirm regarding the interaction between the microstructural
modifications before (as-received conditions TMCP) and after (tempering
treatments). In conjunction with the susceptibility of well accepted that a
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martensitic microstructure induce the decrease of the apparent hydrogen

diffusion rate, favoring greater entrapment and a high concentration of hydrogen
[34]. For this reason it is compulsory to determine the irreversible hydrogen
traps, in order to establish an adequate correlation among all these variables.

Table 4.Permeability test values.

Sample Flux ss Deff Capp
condition (mol/cm².s) (cm²/s) (mol/cm³)
As-received 2.17 E-11 2.88 E-06 7.50 E-06
200°C -1 min 1.06 E-11 1.04 E-06 1.01 E-05
200°C -3 min 1.93 E-11 1.25 E-06 1.53 E-05
200°C -10 min 1.74 E-11 2.27 E-06 7.64 E-06
400°C -1 min 1.18 E-11 1.18 E-06 9.91 E-06
400°C -3 min 2.03 E-11 2.00 E-06 1.01 E-05
400°C -10 min 6.77 E-12 1.13 E-06 5.97 E-06
400°C - 300 min 1.61 E-11 2.26 E-06 7.10 E-06
600°C - 1 min 1.98 E-11 1.70 E-06 1.15 E-05
600°C - 3 min 2.28 E-11 2.06 E-06 1.10 E-05

CONCLUSIONS
In the present experimental microalloyed steel showed a decrease in the
mechanical properties due to the hydrogen embrittlement effect. These have
been attributable to the presence of internal blisters by the accumulation of
hydrogen.
The samples heat treated and charged at 12 hrs, showed variations of the UTS,
YS, always below the mechanical properties of the as-received condition.
At the tempering condition 400°C-10min-hc treated, showed a lower
susceptibility to embrittlement and the lowest Capp value.
The higher susceptibility and the higher reduce values on the mechanical
properties were obtained at: 200°C-3 min, 400°C-3 min, and 600°C-1 min hc-
treated conditions.

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