MM 694: M.

Tech Credit Seminar

Hydrogen Damage in ferrous Alloys and

Prevention
By
Udit Kumar (163110065)

Supervisor
Prof. V. S. Raja

Department of Metallurgical Engineering and Materials Science

INDIAN INSTITUTE OF TECHNOLOGY BOMBAY

(Year 2017)

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 Declaration

I, Udit Kumar (163110065) realize that plagiarism may be a form of:

(a) Wrongful personalization of another authors idea or work without accreditation
(b) Immorality regarding original work
I hereby reiterate that I havent plagiarized. I deeply regret if I have done so
Advertently. I do understand that it may not have been possible for my guide to
delve into the details owing to time constraints.

April, 2016 Signature

Place: Mumbai (Udit Kumar)
163110065
M.Tech Student
MEMS, IIT Bombay

2
 Certificate
It is hereby certified that the seminar report titled Hydrogen Damage in ferrous
Alloys and Prevention is a record of seminar work pursued by Udit Kumar
(163110065) during 2nd semester (2016-17) of M.Tech in Corrosion Science and
Engineering from Metallurgical Engineering and Materials Science Department,
Indian Institute of Technology Bombay.

April, 2017 Professors in charge:

Dr. V. S. Raja
Place: Mumbai
Department of Metallurgical Engineering and
Materials Science
IIT Bombay

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 Acknowledgement

I am deeply indebted to my guide, reverend Dr. V. S. Raja for their immense

contribution towards my seminar. It would not have been possible for me to pursue
this project had it not been for their inspiration and constant support throughout my
work. I would take this opportunity to thank my colleagues and friends, discussions
with them was an immense support and resource. I would like to thank staffs and
team of Central Library, IIT Bombay, without the resources made available by them
this seminar would be impossible.

Udit Kumar
163110065
M.Tech Student
MEMS, IIT Bombay

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 Abstract

Hydrogen damage (HD) in ferrous alloys /steels is an extensively observed

phenomena (as early as 19th century) and very common in hydrogen damage prone
industries. Hydrogen blistering (HB), hydrogen embrittlement (HE) and high-
temperature hydrogen damage are the main classifications, among which HE
mechanism is still ambiguous (many models are proposed). Prevention techniques
for HD involve material selection, improvement of environment etc. Trapping sites
for hydrogen atom have been explored to prevent HE, the alloying addition of a
hydride forming element (Ti, Zr, Hf) in iron/steel matrix has been considered as
trapping site. Apart from trapping at atoms (Ti) or (TiC) particle, there is the
possibility of precipitating out Ti as titanium hydride which will also give
precipitation hardening. Concentration of titanium added must take into account the
fact, excess will result in hydrogen embrittlement of 2nd type (titanium hydride acting
as crack initiation site).

Keywords
Hydrogen Damage, Hydrogen Embrittlement, Hydrogen Blistering, Titanium, adnn
Steels

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List of Figures

S.No. Fig.No. Figures Page

No.
1 2.1 Hydrogen Blistering in a carbon steel plate 10
2 2.2 Mechanism of Hydrogen blistering step wise process 11
3 2.3 Iron-Hydrogen phase diagram 12
4 2.4 Schematic diagram of hydrogen embrittlement by HEDE 12
5 2.5 Schematic of HEDE mechanism 13
6 2.6 Schematic diagrams illustrating hybrid mechanisms of 14
hydrogen-assisted cracking
7 3.1 Mechanisms available for the modification of steel to 15
better resist hydrogen
8 4.1 Schematic illustration of hydrogen trap site at (a) 17
9 5.1 Solubility of hydrogen in iron matrix with different 20
alloying additions
10 5.2 Iron Titanium Phase diagram 21
11 5.3 Titanium Hydrogen Phase Diagram with varying 22
pressure
12 5.4 Titanium Hydrogen phase diagram(atmospheric 23
pressure)
13 7.1 NACE Standard Tensile Test 25
14 7.2 NACE Schematic arrangement for bending beam test 26
15 7.3 Schematic Setup for hydrogen embrittlement testing 27
used by G. Tiwari et al. [4]

List of Tables
S.No Table Table Page
No No.
1 4.1 Hydrogen trapping energies by substitutional solid 19
solution alloying additives in steel

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Abstract 5
List of Figures 6
6
List of Tables
Table of Contents

S.No. Title Page

no.
1) Introduction 8
1.1) Hydrogen damage in Steels 8
1.1.1) Hydrogen Blistering 8
1.1.2) Hydrogen Embrittlement 9
2) Mechanism of Hydrogen damage 10
2.1) Hydrogen Blistering 10
2.2) Hydrogen Embrittlement 11
3) Hydrogen damage prevention in Steels 15
4) Hydrogen trapping in Steels 17
4.1) Reversible Trap 18
4.2) Irreversible trap 18
5) Hydrogen embrittlement prevention by using Titanium(or hydride 20
forming metals) as trap site
5.1) Titanium-Hydrogen phase diagram 21
6) Hydrogen embrittlement due to Hydride formation & precipitation 24
hardening by Hydride formation in Titanium alloys.
7) Laboratory tests for Hydrogen Embrittlement 25

7.1) NACE Standards. 26

7.2) Other setups 26
8) Characterization techniques 28
9) Conclusions 29

References

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 Chapter 1: Introduction

Hydrogen damage in ferrous alloys/steel is widely discussed and studied topic, as different grades
of steel is the most important industrial material till today since its inception. Ferrous alloys/steels
used in hydrogen damage prone industries and applications are susceptible to it. When
steels/ferrous alloy structure is subjected to constant or varying stress condition with hydrogen
intensive environment they show hydrogen damage by various mechanisms. Hydrogen blistering
and hydrogen embrittlement is the two main category to classify those failures especially in steels
and ferrous alloys. In this report I have considered hydrogen damage at low temperature, high
temperature hydrogen damage such as decarburization and hydrogen attack are not the part of
present discussion. Hydrogen atom diffusion through the iron matrix, trapping of H atoms in
matrix, classification of trapping are discussed in perspective to find a solution to hydrogen
damage in steels. Methods of hydrogen damage prevention have been discussed. Titanium as
alloying addition to prevent hydrogen damage has been considered, it is basically combining the
two different type of hydrogen damage reportedly, delayed cracking in hydride forming metals
(Ti, Zr) and hydrogen embrittlement due high concentration of H atom in metal matrix. (Fe).
Method combineing these two features and suggest to restrict concentration of Ti in Iron matrix to
the point Titanium hydride doesnt act as a crack initiation site. Testing methods for hydrogen
damage is also discussed (NACE standards and other setups), briefly characterization techniques
are also discussed.

1.1) Hydrogen damage in Steels

1.1.1) Hydrogen Blistering (Hydrogen Induced Cracking HIC)

Hydrogen induced cracking also known as stepwise cracking, cracking parallel to the surface of
steel plate because of the stress generated due to formation of molecular hydrogen from the
absorbed atomic hydrogen. Stepwise cracking occur if inclusions are available at varying depths
along the thickness of steel sample. This is not get affected by PWHT. HIC resistant steel is
developed to address this issue, NACE TM0284-87 standard is used to test HIC resistant steels.

Stress-Oriented Hydrogen Induced cracking (SOHIC)

A special form of HIC or Blistering, array of small fissures of small hydrogen cracking in the
sample which are perpendicular to the applied stress (generally in H2S environment). NACE
TM0284-87 standard test for qualification of steels for SOHIC resistance. PWHT isnt very
effective in this case also.

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1.1.2) Hydrogen Embrittlement
Hydrogen embrittlement is the process by which metals such as steel become brittle and fracture
due to the introduction and subsequent diffusion of hydrogen into the metal. Hydrogen
embrittlement occurs in a number of forms but the common features are an applied tensile stress
and hydrogen dissolved in the metal. Examples of hydrogen embrittlement are cracking of
weldments or hardened steels when exposed to conditions which inject hydrogen into the
component. Presently this phenomenon is not completely understood and hydrogen embrittlement
detection, in particular, seems to be one of the most difficult aspects of the problem. Hydrogen
embrittlement does not affect all metallic materials equally. The most vulnerable are high-strength
steels, this is often a result of accidental introduction of hydrogen during forming and finishing
operations.

Sulphide Stress cracking

Sulphide Stress Cracking (SSC) also called hydrogen stress cracking or hydrogen embrittlement
cracking. Crack formation due to hydrogen concentration beyond critical limit or hydrogen
charging in high strength hardness steel. That is why in some industries (especially petroleum
industry) hardness and strength of steel is limited (200 BHN hardness & 620 MPa) to prevent
cracking. NACE RP0472-87 standard deals with above mentioned case, post weld heat treatment
(PWHT) are done to remove this.

Hydrogen Damage at high temperature

Decarburization and hydrogen attack arent the part of present discussion, but they are also a
serious problem. At high temperature hydrogen diffuses into the matrix combine with the carbon
atoms (in solid solution with iron) of carbide particle to form methane gas and stress generation
leads to cracking. The methane gas is not mobile and collects in small voids along the grain
boundaries where it builds up enormous pressures that initiate cracks.

To address the problem of hydrogen embrittlement, emphasis is placed on controlling the amount
of residual hydrogen in steel, controlling the amount of hydrogen pickup in processing, developing
alloys with improved resistance to hydrogen embrittlement, developing low or no embrittlement
plating or coating processes, and restricting the amount of in-situ (in position) hydrogen introduced
during the service life of a part.

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 Chapter 2: Mechanism of Hydrogen damage

To understand Hydrogen damage in steel we need to consider the solubility of hydrogen in steels,
Study carried out by Oriani et al. has proposed [2] based one previous data has proposed empirical
relationship for solubility of hydrogen in matrix with respect to temperature (eqn no.2.1)
C0 = 0.00185P exp (-3440/T) [2.1]
For the temperature range 282 to 910 C0. at atmospheric pressure. Empirical relationship for
temperature range 49 to 506 C0 has also been proposed.

2.1) Hydrogen Blistering

Hydrogen penetration in metal results in blistering of metal. A cross-section image of hydrogen
blistering is shown in Fig: 2.1.

Fig 2.1: Hydrogen Blistering in a carbon steel plate [21]

Low alloy low or medium carbon steel hydrogen blistering is very common it is also called step
wise cracking. Blistering mechanism involves the stress relaxation in the form of crack, stress
produced due to formation molecular hydrogen inside the matrix or at the inclusions & vacancies.
Hydrogen can reach the defects by both diffusion and dislocation transport [20]. Defects which
have high binding energy of hydrogen tends to accumulate H atoms. This causes concentration of
H atoms increasing at the site then result in molecular hydrogen precipitation. Molecular hydrogen
exerts pressure.
Microstructural discontinuities, for example carbide-matrix interphase boundaries, grain
boundaries, pearlite colony boundaries and secondary phase-matrix interphase boundaries tends to
concentrate hydrogen atoms. However Propagation always doesnt follow the microstructural
features, they may pass through matrix to take maximum shear stress direction.
A simple illustration of blistering mechanism is shown in Fig: 2.2

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 Fig 2.2: Mechanism of Hydrogen blistering step wise process (a), (b), (c) & (d) [22]

2.2) Hydrogen Embrittlement (HE)

Till today there isnt any fully applicable practical model which explain complete mechanism of
hydrogen embrittlement. Unviability of a working model makes us unable to predict hydrogen
damage in metals and take necessary precautions. This is a highly explored field and people have
time and time again come up with mechanisms especially for different kind of steels [2-7].

2.2.1) Hydride formation and fracture

Metals which form hydride extensively such as Ti, Zr, and Ta etc. undergo hydrogen embrittlement
via this mechanism, it is a widely studied and somewhat verified model for those metals. It is
discussed in details in chapter 6.
Generally in steel, hydride doesnt forms at normal or even in aggressive environment.

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 Fig 2.3 Iron-Hydrogen phase diagram 1, 2, 3 are the calculation by different scholars [2]
Delta phase formation does happen at high temperature and high hydrogen concentration at 1bar
pressure but it is out of scope of present discussion.

2.2.2) Hydrogen-enhanced decohesion (HEDE) Description

Fig 2.4: Schematic diagram of hydrogen embrittlement by HEDE [3]

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 Fig: 2.5 Schematic of HEDE mechanism, i) showing H in lattice, ii) hydrogen adsorption, iii)
hydrogen interaction with particle matrix interface.
Hypothesis proposed in support of this mechanism -charge-transfer happen between s orbital of
hydrogen and d orbital of metal which results in weakening of interatomic bonds, which is
decohesion [2]. Decohesion generally manifests as simple tensile separation of atoms, when the
critical crack-tip-opening displacement (CTOD) (approximately half the interatomic spacing) is
reached. Incipient shear movement of atoms needed to enable CTOD, but the separation of atoms
is blocked by surrounding atoms and the separation process is complex. [4] [5]

2.2.3) Hydrogen-enhanced localized plasticity (HELP)

It was proposed that, since hydrogen concentrations were localized near crack tips due to
hydrostatic stresses or entry of hydrogen at crack tips, deformation was localized near crack tips
as a result of solute hydrogen facilitating dislocation activity. It was argued that sub-critical crack
growth should then occur by a more localized micro void-coalescence (MVC) process than that
which would occur in inert environments.

2.2.4) Adsorption-induced dislocation emission (AIDE) Description)

The AIDE mechanism is, in some respects, more complex than the HEDE or HELP mechanisms
For the AIDE model, the term dislocation-emission encompasses both nucleation and subsequent

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movement of dislocations away from crack tip, and it is important to note that it is the nucleation
stage that is critical and facilitated by adsorption. Once nucleated, dislocations can readily move
away from the crack tip under the applied stress. The nucleation stage involves the simultaneous
formation of a dislocation core and surface step by co-operative shearing of atoms (breaking and
re-forming of interatomic bonds) over several atomic distances. Thus, weakening of interatomic
bonds over several atomic distances by adsorbed hydrogen can facilitate the process. [3]

2.2.5) Hybrid mechanisms and possible role of vacancies

Combinations of AIDE, HELP, and HEDE mechanisms could, of course, occur in many cases,
with the relative importance depending on the fracture mode, which depends on the material and
other variables [3][4][5]. For example, dislocations nucleated from crack tips (due to AIDE) may
move away from crack tips more readily due to HELP, thereby decreasing the back-stress on
subsequent dislocation emission. For crack growth predominantly by AIDE, void-nucleation ahead
of cracks could be promoted at slip-band intersections by HELP or by HEDE at particlematrix
interface AIDE and HEDE could also occur sequentially, with AIDE occurring until the back-
stress from emitted dislocations increased somewhat so that HEDE then occurred, followed by
AIDE again when the crack tip had moved away from the stress field of dislocations previously
emitted.

Fig: 2.5 Schematic diagrams illustrating hybrid mechanisms of hydrogen-assisted cracking: (a)
AIDE with contributions from HELP and HEDE, and (b) AIDE alternating with HEDE. [3]

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 Chapter 3: Hydrogen damage prevention in Steels

In order to decrease the hydrogen-induced degradation of steel special attention should be paid to
suppress corrosion processes and hydrogen uptake. In the case of low-carbon, low- strength steel,
the main effort of research and of technology works should be applied in the following directions.
For low carbon steels (Hydrogen Blistering is main source of problem) [2]
Purification of the steel: decrease in H2, O2, S and P content, and of the number of
nonmetallic inclusions;
Modification of molten steel with REM; - heat and mechanical treatment, resulting in
homogeneous and stable microstructures;
Modification of working media: reduction of H2S content, control and increase of pH of
solutions, temperature control, inhibitor additions;
Modification of the surface layer of steel.
Hydrogen embrittlement prevention (prevalent in high strength steels)
Common prevention techniques has been summarized in fig: 3.1.Some of the techniques shown in
fig: 3.1 is applicable to both hydrogen blistering as well as the hydrogen embrittlement

Fig: 3.1 Mechanisms available for the modification of steel to better resist hydrogen [26]

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To address the problem of hydrogen embrittlement, emphasis is placed on controlling the amount
of residual hydrogen in steel, controlling the amount of hydrogen pickup in processing, developing
alloys with improved resistance to hydrogen embrittlement, developing low or no embrittlement
plating or coating processes, and restricting the amount of in-situ (in position) hydrogen introduced
during the service life of a part. HIC resistant steels has been developed which is a high strength
alloy, owing to its strength and alloying addition not prone to hydrogen atom accumulation is
effective in reducing hydrogen damage. There are many varieties of strong hydrogen traps in steels,
but by far the most advanced application of the concept of capturing diffusible hydrogen within
the steel has been in the invention of strong bolting steels that are not susceptible to delayed
fracture. The bolts have been tested for many years in service and demonstrated to outperform
those that do not contain the hydrogen traps. [26] [27]

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 Chapter 4: Hydrogen Trapping in Steel

The immobilization of H atom in iron matrix is called trapping. Trapping can be of two types
reversible and irreversible (will be discussed in details). It basically depend on the energy of the
trap. Vacancies, dislocation core, dislocation, grain boundaries, impurities, alloying addition,
carbides (in high strength steels) etc. can act as a trap site and actually they do, but with different
energies.

(a)

(b)
Fig: 4.1 Schematic illustration of hydrogen trap site at (a) atomic scale (b) microscopic scale [3]

Experimental methods to study trap

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1) Thermodynamic method - A general relationship between chemical potential (u) of trap site
and concentration of H atom associated with it was derived by R Kirchheim [9]

[4.1]
In equation 4.1 n(Gi_)dGi is the concentration of traps of free enthalpy (Gibbs free energy) ranging
from Gi to Gi + dGi_, and C is the total concentration of hydrogen in the metal expressed as the
ratio of the number of hydrogen atoms to the number of interstitial sites of one kind. All the
parameter are measured experimentally and equation 4.1 is solved by using Dirac delta function
[2].
2) Long range order - The major share of examinations on viable diffusivity have been performed
with film formed specimens, with the hydrogen kept as near zero as conceivable on one side and
some non-zero hydrogen fixation on the opposite side. There is an underlying transient period in
which the diffusion flux touching base at the exit side increments with time, followed by a
relentless state stream of hydrogen.
Acting as a sink or source depending upon the concentration of H atom and effective diffusion
coefficients [2]
There are numerous way in which trap sites can be classified for ease it is classified as below

4.1) Reversible Trap

If a particular trap site forms an equilibrium with H atom diffusing through the matrix then it is
called as reversible trap, generally lattice defects, dislocation core, vacancies are reversible
trap[2],[7].

4.2) Irreversible Trap

If the rate constants are small, such that equilibration does not occur for particular stream of
diffusing H atom then it is called irreversible traps. In layman terms under the particular test
condition if a trap can only act as sink and never as source, then the trap is an irreversible trap.
Now the order of trapping strength [2]
Solute atoms > Trapping on sites just below free surface and free surfaces itself > Vacancies and
its clusters > Dislocation cores > strain environments > grain boundaries > interface of precipitate
and matrix > interfaces of inclusion/matrix interfaces > Internal cracks and voids

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Alloying addition (substitutional solid solutions) as a trap sites
Despite the fact that the transport of hydrogen in substitutional solid solutions of Iron base alloy
is normally deciphered so far as basic diffusion, there are signs that hydrogen is caught by a portion
of the alloying components. To begin with, certain iron-based compounds have extensively
brought down diffusivities, higher solubilities, and higher actuation energies of hydrogen
dispersion than iron, and in this manner show highlights normally for trapping. Furthermore, in
various frameworks, the arrangement of hydrogen remote metal buildings have been watched.
Several systems are considered few are discussed below
Titanium It was observed by Pressouyre and Bernstein the trapping energy (activation energy of
reorientation) of Ti atom in a substitutional solid solution of Iron and Titanium is 22.5-27 KJ/mol
[8] In his paper he had classified Ti atom as reversible trap and TiC as irreversible trap and
concluded uniform distribution of Ti atom all over matrix is actually good for prevention of
hydrogen damage. I beg to defer as in his theoretical calculation of trapping tendencies of
secondary particle there isnt any analysis to confirm or deny any formation of titanium hydrides
while charging the sample with hydrogen.
Zirconium By Oriani et al.[2] zirconium also musters similar result with activation energy of
reorientation of Zr atom 24 and 36KJ/mol for H atom.
Table 4.1
Hydrogen trapping energies by substitutional solid solution alloying additives in steel [10]
Alloying Ni Mn Cr V Ce Nb Ta La Nd
Elements
Interaction 8.0 8.7 9.6 15.4 15.4 15.4 94.5 94.5 129
Energy
kJ/mol

BCC iron based alloys has higher trapping energies as compared to FCC iron based alloy [2].

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 Chapter 5: Hydrogen embrittlement prevention by using Titanium
(or hydride forming metals) as trap site.

Solubility and diffusivity of H atom in iron matrix depends on alloying addition as shown in in
Fig: 5.1 solubility of H atom in matrix is maximum with addition of Ti as alloying addition, it is
due to the hydride formation by it (not extensively studied) .

Fig: 5.1 Solubility of hydrogen in iron matrix with different alloying additions [2] [11]
In Fig: 5.2 Ti-Fe system phase diagram has been shown, Ti has solubility in Iron up to approx. 0.5
at low temperature, with greater amount of Ti atom as alloying addition extra concentration will
get deposited on grain boundaries while forming hydride atoms at GB will form the precipitates
1st .

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Fig 5.2: Iron Titanium Phase diagram [13]

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 Fig: 5.3 Titanium Hydrogen Phase Diagram with varying pressure p = 10-katm where k is
varying [13]
In Fig: 5.3 with varying pressure of H atom it gives the amount Titanium hydride formation, the
pressure of hydrogen depends on the aggressiveness of the environment.

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 Fig: 5.4 Titanium Hydrogen phase diagram [14]

In Fig: 5.4 Ti-H phase diagram at atmospheric pressure with varying temperature is given, it shows
different phase of hydrides, for our point of view only precipitation of hydrides is important as in
steels application we dont deal with high concentration of H atom (generally steel fails even at
low concentration).
Hydrogen concentration at different site in matrix (grain boundary, vacancies, defects etc.) has
been calculated with respect to atmosphere and time [2] (atmosphere sample is placed and time of
exposure). As shown in fig: 5.4 at around 50 degree Celsius the percentage of H required for
precipitation of Titanium-hydride is well passed the limit, they have also tried to express H
concentration due to trapping in partial pressure.

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 Chapter 6: Precipitation hardening by Hydride formation in
Titanium alloys & Hydrogen embrittlement due to Hydride
formation

Precipitation hardening of Cu-Ti alloy via aging in hydrogen environment and subsequent
precipitation of Titanium hydrides has been explained and adopted technique [15]. As Titanium
shows two oxidation (2&4) generally, Ti forms TiH2 and TiH4 both with varying temperature and
H to Ti ratio has been discussed in previous chapter. While doing precipitation hardening there are
few critical parameters we need to consider which will decide the strengthening mechanisms. If
coherent secondary phase then coherency strain, if incoherent particle then strengthening by
Orowan mechanism etc.
Parameters of interest while applying this technique
1.) Percentage of Titanium added
2.) Hydrogen partial pressure and also equivalent pressure inside the matrix
3.) Percentage of Titanium forming hydride in the particular environment
4.) Critical size of precipitates for attaining highest strength and also size after which these
secondary particles start contributing to hydrogen embrittlement of 2nd type.
Hydrogen Embrittlement due to formation of excess hydride
It is a common problem in Titanium alloys [16], Titanium has very good corrosion resistance and
also chemical resistance but if we expose Ti alloys to Hydrogen intensive environments the
problem of hydrogen embrittlement start to surface, solubility of hydrogen in Ti decreases with
temperature (already discussed in previous chapter), hydrides which are formed at high
temperature are very brittle at low temperatures.
Using Titanium alloying addition to stop hydrogen embrittlement in steel is a double edged sword
as proposed and discussed in previous chapter. Any such alloy system will need careful calculation
of hydrogen concentration in environment, temperature, critical concentration of Ti after which
our alloy is prone to hydrogen embrittlement of 2nd type.
We can expand this analogy by taking an example of high strength pipeline steels (X60, X80, and
X100) hydrogen embrittlement of these steel where studied by D. Hardie et al. [17]. They have
considered two variables stress applied to the sample and time it survives in particular hydrogen
environment. Now for the time being let us fix the stress and then alloy fails at 5h we can figure
out how much hydrogen diffused into the matrix after failure and also the critical concentration of
hydrogen below which our alloy dont fail by hydrogen embrittlement mechanism.
Now by taking the difference of hydrogen atoms diffused into matrix critical safe hydrogen
concentration, we can get excess hydrogen atom in matrix we need to immobilize those atom to
reduce the damage. As per already proposed solution (previous chapter) we need to form that much
Titanium hydride and all the titanium atoms added to Fe matrix wont be able to form hydride the
ratio would also be very important.

24
 Chapter 7: Laboratory tests for Hydrogen Embrittlement

7.1 NACE Standards

1) NACE TM0177, 2016 Testing method for resistance to (SSC) Sulfide Stress Cracking and
Stress corrosion cracking in H2S environment. This test comprises methods for testing metals and
alloys by tensile, C ring, double cantilever beam and bent beam. Schematic diagram of testing
setup is shown in Fig: 7.1 and Fig: 7.2. NACE standards are followed to make sure similar testing
conditions and compare different samples. All the details of the standards can be referenced from
[18]. It elaborates test reagents, environment cracking variability and solutions, material
properties, test vessels and fixtures, and testing at elevated temperature/pressure.

Fig: 7.1 NACE Standard Tensile Test [18]

25
 Fig: 7.2 NACE Schematic arrangement for bending beam test [18]
2) NACE Standard - 01018 HYDROGEN EMBRITTLEMENT STRESS CORROSION [19]
Hydrogen embrittlement stress corrosion cracking test performed on duplex steels. A series of tests
was performed to establish the threshold condition for cracking. The tests included: (i) Constant-
load smooth bend tests, (ii) Constant-deflection smooth bend tests, (iii) Constant-load pre-cracked
bend tests, (iv) Interrupted slow strain rate tensile tests, (v) constant-load tensile tests, (vi)
Approximately constant-strain tensile tests and (vii) Full-scale hub tests.
3) NACE - 99433 SOHIC TESTING METHOD
4) NACE - 08109 Effect of NACE TM0284 for on the HIC Performance on Large-Diameter
Pipes

26
7.2 Other setups

Fig: 7.3 Schematic Setup used by G. Tiwari et al. [4]

In Fig: 7.3 a schematic diagram of hydrogen embrittlement test is given, you can see the loading
mechanism and the sample in inside controlled environment.

27
 Chapter 8: Characterization techniques

As already discussed setups for hydrogen damage testing. After metallic samples were subjected
to stress as well as the particular environmental condition failure (partial or complete) happens; it
is very important to characterize the fracture surface, cracks etc. to understand the extent of
damage. It is very important in the study of mechanism of hydrogen embrittlement.
Light Microscope
Primary and foremost tool to examine corroded sample, discussing in detail about the working of
light microscope would be trivial and out of scope of present discussion. Post failure process
metallic sample is cut perpendicularly to fracture surface, to show the cross-section and etched
using nital as etchant. [25]
XRD Analysis
In case of structural changes, de-alloying, formation of new phases during corrosion process XRD
analysis is very important and handy non-destructive technique for characterization.
SEM Analysis
Fracture surface analysis, different mechanism which has been proposed can be studied and
determined using SEM analysis. In situ SEM has also been developed to study the mechanism of
failure.[24]
Nano-Indentation
Besides observations of the effects of hydrogen on slip characteristics around indentations, load-
depth and load-time data obtained from Nano-indentation tests on hydrogen-free and hydrogen-
charged material can also provide information on hydrogen effects during deformation [3]. For
example, for nickel single crystals (with a {111} surface) introducing hydrogen into specimens
decreased the pop-in load (under increasing loads) and decreased the pop-in time (under constant
load). Hydrogen could be introduced and removed electrochemically, and the effects on pop-in
were reversible, suggesting that they were intrinsic ones associated with solute hydrogen. Oxide-
film effects could be discounted, and the results were explained on the basis that solute hydrogen
reduced the shear modulus and facilitated the homogeneous nucleation of dislocations in a volume
of material underneath the indenter.[3]
TEM Analysis
TEM: As per our proposed solution and after performed any of the above mentioned tests, we can
expect small precipitates of TiH2 or TiH4 at high resolution TEM micrograph. TEM as a technique
to analyze failure surface is very valuable. People have used TEM to study hydrogen trapping,
secondary precipitates, studying mechanism of hydrogen embrittlement.[3][4][17].

28
 Chapter 9: Conclusions

Hydrogen damage types and mechanisms are discussed, underline cause of failure would be the
increase localized concentration of hydrogen in iron/steel matrix which can have enhanced
plasticity or induce brittleness in the steel (other mechanism are also discussed). To address the
problem by alloying addition, Titanium would be a suitable element. It forms lot of trap sites in
Fe-Ti-C system. It also has the potential to form Titanium-hydride and take the hydrogen atom out
of matrix and also provide precipitation hardening. Ti as the alloying addition to improve hydrogen
damage resistance of steel lacks proper study and very little literature was available in this regard.
However one study reported to have improved hydrogen embrittlement resistance but failed to
comment on the mechanism. I would like to propose this as an opportunity for future work.

29
References

[1] Merrick, R. D. "An overview of hydrogen damage to steels at low temperatures." Mater.
Performance ;( United States) 28.2 (1989): 53-55.
[2] Oriani, Richard. "Hydrogen degradation of ferrous alloys." Noyes Publications, Mill Rd. at
Grand Ave, Park Ridge, New Jersey 7656, USA,1985. 886 (1985).
[3] Raja, V. S., and Tetsuo Shoji, eds. Stress corrosion cracking: theory and practice. Elsevier,
2011.
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