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Article history: In the present study, a new small punch test (SPT) methodology has been used to analyse the effect of
Received 30 June 2016 hydrogen embrittlement on the tensile properties of three different grades of CrMoV steel: the base metal
Revised 5 September 2016 (CrMoV-1), weld metal (CrMoV-2) and this same weld metal subjected to an intermediate heat treatment
Accepted 9 September 2016
(CrMoV-3). SPT results were compared with those obtained in standard tensile tests carried out in a
Available online 14 September 2016
hydrogen environment. Moreover, a new SPT methodology was used to analyse the environmental effects
on a CrNiMn steel under cathodic protection and cathodic charge.
Keywords:
Results obtained shows the usefulness of the SPT to estimate the grade of deterioration induced by
Small Punch Test (SPT)
Hydrogen Embrittlement (HE)
hydrogen embrittlement, especially when a lack of testing material makes impossible the test of standard
Stress Corrosion Cracking (SCC) specimens.
Ó 2016 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tafmec.2016.09.005
0167-8442/Ó 2016 Elsevier Ltd. All rights reserved.
90 T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100
Fig. 1. Microstructures in L-T orientation in every case of (a) CrMoV-1, (b): CrMoV-2 (identical to CrMoV-3), and (c) CrNiMn R5 grade high-strength steel.
Fig. 2. Custom devices for testing in hydrogen environment: (a) SPT device and (b) tensile device.
in order to achieve similar hydrogen concentrations as those Being E the Young Modulus.
achieved in the small punch specimens. 1=4
0:5 mm
Expressions (1)–(3) were used for estimating the tensile proper- K Jth25 ðMPa m1=2 Þ ¼ K min þ ðK Jth K min Þ ð6Þ
25 mm
ties by means of SPT, in both air and hydrogen environment. Py was
calculated as the intersection between the SPT curve and a straight Being K min ¼ 20 MPa m1=2 .
line running parallel to the initial elastic slope with an offset of In order to apply Lacalle’s model [6], yield stress is necessary. It
t/10, where t is the initial specimen thickness [9,10]. Pm is the max- doesn’t differ much from the value of the as received material [8],
imum test load and dm the displacement at maximum load. but accurate values can be estimated using the expression (7) also
Py proposed in [6], or the previously presented expression (1):
rys ¼ a t=10
ð1Þ
t2 rys ðMPaÞ ¼ 5:75 Py ðNÞ ð7Þ
Pm Being P y the first inflexion point of the Load - Punch displace-
rut ¼ b1 2 ð2Þ
t ment record [6].
Pm The analysis was carried out in two different environmental
rut ¼ b2 ð3Þ conditions: cathodic protection and cathodic charge. For each
ðdm tÞ
one, two different levels of aggressiveness were studied. Cathodic
protection, is usually applied in the accessible parts of the plat-
3.2. Fracture mechanics forms or the off-shore structures. The second one, known as catho-
dic charge or anodic polarization, reproduces local aggressive
For conventional fracture mechanics tests, an analysis was car- environments impossible to avoid, an sometimes to predict, that
ried out obtaining the stress intensity factor, KEAC, employing the can seriously affect the structural integrity of the component
methodology based on the GE-EPRI procedure [12]. exposed. Fig. 3 shows a schema of the two main methods used to
For small punch tests, Lacalle’s methodology [6] was employed study Hydrogen influence in steels, used in this work [1].
in order to obtain the fracture toughness of the embrittled material, The technique of cathodic protection is used to avoid corrosion
JIth. It consists on the determination of the CTOD value, dSPi, that phenomena for marine water environments. Basically, it involves
marks the initiation by means of SPT tests on notched specimens, the use of a sacrificial anode of aluminum (more active than steel),
from which the value of JIC is determined and transformed into which in presence of seawater is connected to the steel structure,
the crack initiation intensity factor, KJth (expression (5)). After that, which is the cathode that will be protected from corrosion [1]
as stated in [8], in order to compare this value with the results of due to the imposition of a fixed potential, which will maintain
KEAC obtained from conventional tests in 25 mm CT specimens, KJth the stability of the process. For cathodic protection the solution
was expressed into its equivalent factor obtained from 25 mm sam- was consisting of marine water simulated having a 3.5% in weight
ples, KJth25, following the expression (6) [13]. Due to the lack of lit- dissolution of NaCl in distilled H2O. Aluminum was used as an
erature to obtain equivalent stress intensity factors in function of anode, and the reference electrode employed contained an Ag/AgCl
the sample thickness the expression (6), even if [13] had just been solution. The pH was controlled at the range 5.5–5.7 during the
evaluated for ferritic steels up to 825 MPa of yield strength, is con- whole tests, at room temperature. Two levels of cathodic protec-
sidered accurate enough for the present high-strength steel that tion (aggressiveness) were analyzed: 950 mV and 1050 mV of
had a ferritic base before being heat treated. fixed potential.
dSPi rys The technique of cathodic charge is used against the phenom-
J Ic ¼ ð4Þ ena that occurs in more aggressive environments (hydrogen trans-
dn
port infrastructures), or to reproduce local situations where a huge
Being dn an adimensional factor [6].
amount of hydrogen is present. It consists in the interconnection,
Being dSPi the CTOD value that marks the crack initiation on a
via an acid electrolyte, of a noble material (platinum in this case)
SPT notched sample [6].
and the steel, which will passivate and receive protection due to
pffiffiffiffiffiffiffiffiffiffiffi the fixed current interposed [1]. For cathodic charge, environmen-
K Jth ¼ J Ic E ð5Þ tal conditions were simulated by using the same electrolyte
92 T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100
Fig. 3. Schematic representation [1] of Left: cathodic protection, Right: cathodic charge.
Fig. 5. (a) Fracture of specimens tested in air, (b) fracture of CrMoV-2 tested in hydrogen, (c) microvoids observed on specimens tested in air and (d) fracture surface of
CrMoV-2 tested in hydrogen.
Table 3
SPT results (mean ± standard deviation).
Fig. 10 and the upper part of Table 4 show the results of the
fracture mechanics tests performed on CT specimens. In the less
aggressive cathodic protection cases (950 mV), the maximum
load of the test machine was reached before showing any notice-
able crack propagation, so it was impossible to predict the KEAC
value, giving as results the lower bound corresponding to the KI
values at that maximum load. From previous results, as attested
in the bibliography [11,15], it could be observed that the more
aggressive the test conditions are lower is the value of KEAC. As a
consequence of this, it can be observed that if a cathodic protection
Fig. 7. CrMoV-3 specimen fully cracked just after Py (test stopped at 500 N). or cathodic charge scenario is fixed (a dissolution and a solicitation
Fig. 8. CrMoV-1 broken specimens: (a, b) Tested in air and (c, d) tested in hydrogen.
Fig. 9. (a) CrMoV-2 broken specimen and (b) detail of the fracture surface.
T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100 95
Table 4 slower of 0.002 mm/s. In the lower part of Table 4 the numerical
Results of conventional and SPT fracture tests. results of the previous tests are summarized, obtaining the fracture
parameter KJth25 (in order to be compared to the 25 mm think C.T.
Rate KIEAC or KJth25 value specimens results). Regarding the experimental curves there can
Environment
(mm/s) (MPa.m1/2)
be found typologies from ductile, such as those from 950 mV
Fracture 6E-8m/s 32.80
5mA/cm2 cathodic protection environments, to brittle ones, such as those
Mechanics tests 6E-9m/s 30.92
6E-8m/s 46.04 from 5 mA/cm2 cathodic charge environments. It is easy to distin-
1 mA/cm2 guish how the curve’s shape becomes more typical from a brittle
Cathodic Charge 6E-9m/s 36.69
Fracture 6E-8m/s 138.26 material as the environment becomes more aggressive, this fact
-1050mV
Mechanics tests 6E-9m/s 117.28 means that as the hydrogen content must be higher (as it will be
6E-8m/s >140 checked later by H2 contents measurement tests). It is also
-950mV
Cathodic Protecon 6E-9m/s >120 observed that the more aggressive the environment is the lower
the values of the load (P) and punch displacement (d) of the max-
0.010mm/s 84.25 imums of the curve are. This fact is also an evident marker of a
Small Punch
5mA/cm2 0.002mm/s 75.77
Tests higher Hydrogen content (checked by H2 contents measurement
5E-5mm/s 61.72
0.010mm/s 111.84
tests) and a lower value of the fracture parameter, which is in
Cathodic Charge accordance with experimental standard tests results [8,15].
1mA/cm2 0.002mm/s 110.41
5E-5mm/s 68.41 Fig. 12 shows fracture SEM images of the notched specimens
0.010mm/s 162.33 pre-embrittled and subsequently tested in air. Two samples are
Small Punch
-1050mV 0.002mm/s 131.57 shown; one belongs to a specimen tested in the most adverse envi-
Tests
5E-5mm/s 116.65 ronment (acid solution at 5 mA/C m2 at 0.002 mm/s), the other
0.010mm/s 161.43 becomes from a test in the less aggressive environment (saline
Cathodic Protecon
-950mV 0.002mm/s 134.00 solution at 950 mV at 0.01 mm/s). It can be observed how the
5E-5mm/s 118.47 sample corresponding to the most adverse environment, whose
curves have a typical brittle shape, also have a brittle fracture
showing short crack tip opening (indicating short CTOD and tough-
rate are fixed), if the applied intensity (or potential) is increased ness). On the other hand, the sample belonging to the least aggres-
the value of KEAC will decrease. On the other hand, for a fixed dis- sive environment, whose curves have a typical ductile shape, show
solution and intensity (or potential), if the solicitation rate is a ductile fracture with an important crack tip opening (indicating
decreased the value of KEAC will decrease. higher CTOD values and toughness).
Fig. 11 presents the curves registered from the SPT tests carried Fig. 13 presents the curves registered from the SPT tests carried
out on notched specimens in order to determine the fracture prop- out on notched specimens in order to determine the fracture prop-
erties of the material after hydrogen absorption testing them in air. erties of the material after hydrogen absorption testing them in the
Tests were carried out at two different loading rates, the regular same environment. Tests were carried out at the loading rate of
one of 0.01 mm/s recommended by [5] and another one 5 times 5 105 mm/s recommended by [7]. In the lower part of Table 4
96 T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100
Fig. 11. SPT curves of pre-embrittled samples tested in air at regular rates.
Fig. 12. SEM images of SPT specimens pre-embrittled and subsequently tested in air; Left: test in cathodic charge environment in acid solution at 0.002 mm/s under 5 mA/
cm2 of current imposed (the most aggressive environment), Right: test in cathodic protection environment in saline solution at 0.01 mm/s under 950 mV of potential
imposed (the less aggressive environment).
T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100 97
Fig. 13. SPT curves of samples embrittled and tested in environment at a very low rate.
Fig. 14. SEM images of SPT specimens embrittled and tested in the aggressive environment at a very low rate of 5 105 mm/s; Left: test in cathodic charge environment in
acid solution at 5 mA/cm2 of current imposed (the most aggressive environment), Right: test in cathodic protection environment in saline solution at 950 mV of potential
imposed (the less aggressive environment).
98 T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100
the numerical results of the previous tests are summarized, obtain- the fracture parameter by SPT test previously exposed. Regarding
ing the fracture parameter KJth25. Regarding the experimental the comparison of two different loading rates for the same environ-
curves all typologies presented have a brittle aspect, but those from ment lower values of KJth25 are obtained for lower punch displace-
the most aggressive environment of 5 mA/cm2 cathodic charge ments rates, and also fixing a punch rate lower values of KJth25 are
have a more brittle shape than those others from the less aggressive obtained for more aggressive environments. These facts, added to
one of 950 mV cathodic protection. Also in this case, the more the different shapes of the curves, mean that the Small Punch test
aggressive the environment is the lower the values of the load (P) performed in adverse conditions can show the effect of the punch
and punch displacement (d) of the maximums of the curve are, loading rate on the specimen.
meaning a higher Hydrogen content and a lower value of the frac-
ture parameter [8,15]. In both cases, comparing to its homologous
in Fig. 11, curves shapes are more brittle, due to the lower rate
and the continuous H2 diffusion to the crack tip that permits the
Hydrogen damage capacity to produce its complete effect.
Fig. 14 shows fracture SEM images of the notched specimens
embrittled and tested in the aggressive environment at a very low
rate of 5 105 mm/s [7]. Two brittle samples are shown; one
belongs to a specimen tested in the most adverse environment (acid
solution at 5 mA/C m2), the other becomes from a test in the less
aggressive environment (saline solution at 950 mV). It can be
observed how the sample corresponding to the most adverse envi-
ronment, whose have the most brittle shape, also have an extre-
mely brittle fracture showing a very slightly crack tip opening. On
the other hand, the sample belonging to the less aggressive envi-
ronment, shows also brittle fracture with a higher crack tip opening
than the previous ones. In both cases, comparing to its homologous
in Fig. 12, fractures are more brittle, due to the lower rate and the
continuous H2 diffusion to the crack tip that permits the Hydrogen
damage capacity to produce its complete effect.
In Fig. 15 is shown a comparison between the values of KEAC
Fig. 16. Trend between fracture mechanics and SPT.
obtained by fracture mechanics tests and the two approaches of
It can be observed in Fig. 16 that both techniques can predict First, it was demonstrated that SPT can be a very useful tool to
embrittlement using SPT, giving correct trends when compared estimate the deterioration of structural steels due to hydrogen
to fracture mechanic tests. In the trends presented in Fig. 16, the embrittlement, in terms of tensile properties. Nevertheless, the
values corresponding to the tests at 950 mV of cathodic protec- aggressiveness of the test environment has to be properly selected,
tion have been dashed for a better accuracy, due to the fact that a more profound study of this issue is still necessary in order to
the results of KIEAC from standard fracture mechanic tests (see obtain universal relationships between results obtained in SPT
Fig. 10) could just be calculated as a lower bound at the point that and in standard tensile tests.
the machine reached its maximum load capacity. The previous Moreover, regarding fracture mechanics, by comparing the SPT
results show that the SPT tests performed in an adverse shows in different environments and different loading rates, it was proved
qualitatively correct results in aggressive environment that the test is able to show the effect of the environment on the
characterizations. material, as well as the effect of punch displacement rate varia-
Hydrogen determination tests were also performed on the tions. By comparing the SPT with standard crack propagation tests,
CrNiMn steel. The obtained results are presented in Fig. 17. Hydro- it was proved that the SPT gives qualitatively correct results in
gen concentrations were measured just after the embrittlement, aggressive environment characterizations, although tests per-
after 5 min exposition and after 10 min exposition (times neces- formed in air after being hydrogen pre-charged are not able to give
sary to perform tests under punch displacement rates of accurate results. This fact might be explained by differences at the
0.01 mm/s and 0.002 mm/s). As a comparison tool, the intrinsic crack tip in terms of strain rate and hydrogen diffusion and
hydrogen content of CrNiMn R5 grade steel is also represented accumulation.
by a horizontal line in the same graph. It can be observed that The issue to be solved in a future work concerns the displace-
the more aggressive the environmental conditions are, the higher ment rate that should be employed in SPT tests in order to accu-
is the Hydrogen concentration. It is also noticeable that the highest rately reproduce the environmental conditions taking place
hydrogen concentration rate of decrease takes place during the during a conventional standard test. Important attention should
first minutes of the sample being exposed to air. The previous H2 be played to the circumstances involving what is taking place at
content results are in agreement with the experimental SPT curves, the crack tip in terms of deformation rate and hydrogen diffusion.
when the curve’s shape becomes more typical of a brittle material It seems that the whole test must be performed in similar condi-
the hydrogen content gets increased. tions to those present in conventional crack propagation tests in
The curves in this work have been from ductile curves, such as order to obtain the good results. A quasi-static displacement rate
those from 950 mV cathodic protection environments holding should be used, while the specimen remains submerged into the
hydrogen contents of approximately 1–2 ppm, to fragile curves hydrogen environment, which will definitely reproduce the same
as those from 5 mA/C m2 cathodic charge environments showing micromechanisms that take place at the crack tip during conven-
hydrogen contents of approximately 4–5.5 ppm. It is also observed tional tests.
that once the hydrogen content of the material reaches a high Another type of approach, such as an energetic one, could also
value between 3 ppm and 5 ppm (as occurs in 5 mA/C m2 and be studied in order to find more accurate estimations [16]. In
1 mA/C m2 cathodic charge environments), the hydrogen trapped [16] it is analyzed how load-punch displacement recordings from
in the microstructure is sufficient to produce cleavages at the crack embrittled and non-embrittled SPT notched specimens are coinci-
tip without the need for these to be exposed to a continuous source dent up to a point, where a certain level of energy is reached,
of hydrogen, thus leading to crack propagation under hydrogen showing the embrittled one a decrease after it. This fact justifies
embrittlement. the environmental effect on the crack initiation when that certain
level of energy is reached, meaning that the embrittlement damage
5. Summary and conclusions initiates due to the environmental effect in that point.
In this paper, the small punch test has been validated as a Acknowledgments
method for characterizing materials under stress corrosion crack-
ing and hydrogen embrittlement scenarios, and some basic guide- The authors of this paper would like to thank the Spanish Min-
lines have also been established to perform this characterization. istry of Economy and Competitivity for the support received for the
100 T.E. García et al. / Theoretical and Applied Fracture Mechanics 86 (2016) 89–100
development of the research projects MAT2011-28796-C03: [8] B. Arroyo, J.A. Álvarez, R. Lacalle, F. Gutiérrez-Solana, T.E. García,
Environmental effects on R5 steel under cathodic protection and cathodic
‘‘Metodologías para la caracterización de materiales metálicos en
charge. Characterization using the small punch test, in: Proceedings of the 2nd
condiciones ambientales adversas mediante ensayos Small Punch” SSTT, Austria, 2014.
and MAT2014-58738-C3: ‘‘Efectos del hidrógeno en la tenacidad a [9] T.E. García, C. Rodríguez, F.J. Belzunce, I. Peñuelas, B. Arroyo, Development of a
la fractura y fatiga de aceros de media y alta resistencia para su uso methodology to study the hydrogen embrittlement of steels by means of the
small punch test, Mater. Sci. Eng., A 626 (2015) 342–351.
en contacto con hidrógeno a presión y con medios acuosos ácidos” [10] T.E. Garcia, C. Rodríguez, F.J. Belzunce, C. Suárez, Estimation of the mechanical
(SAFEHIDROSTEEL). properties of metallic materials by means of the small punch test, J. Alloy.
Compd. 582 (2014) 708–717.
[11] J.A. Álvarez, Fisuración inducida por hidrógeno de aceros soldables
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