10 1016@j Ijhydene 2020 01 104

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
ScienceDirect
journal homepage: www.elsevier.com/locate/he
Effect of PTFE coating on enhancing hydrogen

embrittlement resistance of stainless steel 304 for
liquefied hydrogen storage system application
Jae-Sik Hwang, Jeong-Hyeon Kim, Seul-Kee Kim, Jae-Myung Lee*

Department of Naval Architecture and Ocean Engineering, Pusan National University, Busan, 46241, South Korea
highlights graphical abstract
The effects of polytetrafluoro-

ethylene coating on hydrogen
embrittlement are tested.
Charpy V-notch impact tests were
carried out after hydrogen pre-
charging.
Hydrogen concentration, EBSD and
SEM analysis were conducted on
tested samples.
The polytetrafluoroethylene
coating had positive effects on the
toughness reduction.
article info abstract
Article history: The phenomenon of hydrogen embrittlement phenomenon is known to be a major

Received 12 November 2019 obstacle to proposed to overcome this phenomenon. In the present study, polytetra-
Received in revised form fluoroethylene (PTFE), which is known to be an effective hydrogen adsorption and
10 January 2020 desorption material, was coated on the surface of stainless steel 304 to improve its
Accepted 15 January 2020 hydrogen embrittlement resistance. To make a hydrogen embrittlement environment,
Available online xxx electrochemical hydrogen pre-charging was applied to the PTFE-coated stainless steel 304.
To investigate the effects of PTFE coating on the hydrogen embrittlement resistance of
Keywords: stainless steel 304, the Charpy V-notch impact (CVN) test was performed under three
Hydrogen embrittlement different temperatures: 25, 83, and 196 C. Additionally, hydrogen concentration, elec-
PTFE coating tron back scatter diffraction (EBSD), and scanning electron microscopy (SEM) evaluations
CVN impact test were carried out to verify the results of the CVN impact test. The PTFE coating did not have
Hydrogen pre-charging a significant effect on the quantitative reduction of hydrogen concentration; however, we
confirmed its excellent performance in terms of toughness reduction due to the increase in
hydrogen loading time at room temperature.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author.
E-mail address: jaemlee@pusan.ac.kr (J.-M. Lee).
https://doi.org/10.1016/j.ijhydene.2020.01.104
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Hwang J-S et al., Effect of PTFE coating on enhancing hydrogen embrittlement resistance of stainless steel 304
for liquefied hydrogen storage system application, International Journal of Hydrogen Energy, https://doi.org/10.1016/
j.ijhydene.2020.01.104
2 international journal of hydrogen energy xxx (xxxx) xxx
Austenitic stainless steels of the 300 Series have excellent

Introduction material properties at cryogenic temperatures, and are re-
ported to be less susceptible to low-temperature brittleness
Hydrogen is attracting increasing attention amount of atten- [7,8]. In addition, these materials have been reported to be
tion as a next-generation energy source, because it is envi- resistant to crack growth, due to their capacity to undergo
ronmentally friendly and an unrestricted resource. Hydrogen phase-transformations to martensite at low temperatures,
by-products resulting from the use of hydrogen in a fuel cells thereby having excellent properties in terms of fracture due to
consist solely of water, and, when combusted, its generation fatigue [9]. As a result of these advantages, 300 Series
of pollutants, other than minimal quantities of nitrogen, is austenitic stainless steels are being widely used in the ship-
zero. As a result of these advantages, the global demand for building industry, for instance in liquified natural gas cargo
hydrogen is steadily increasing, and in 2050, the market share containment systems (LNG CCS), which are required to func-
of hydrogen is expected to be the largest in the energy market tion in extreme environments (163 C, 25 kPa). Moreover, the
[1]. However, hydrogen gas presents a high risk of explosion, 300 Series austenitic stainless steels studied in cryogenic
due to the temperature range over which it becomes flam- research have also been used as materials for evaluating
mable; furthermore, the phenomenon known as hydrogen hydrogen embrittlement resistance (HER). The present eval-
embrittlement (HE) is a major drawback and emerging prob- uation pertains to the application of stainless steel in
lem in the use of hydrogen energy. hydrogen storage tanks’ primary barrier. HE and cryogenic
HE occurs when hydrogen is diffused into metals and conditions were generated by charging with high-pressure
weakens the bonding forces between the metal's bonds, this hydrogen and injecting helium gas; then, evaluation of the
can lead to hydrogen delayed fracture and degradation of the HER was conducted through tensile tests. As a result, it was
toughness or ductility of the metal. Several studies over the confirmed that the elongation rate of stainless steels 304 and
past decades have reported up the HE phenomenon [2e4], and 304 L were greatly decreased by the influence of hydrogen at
several mechanisms have been discovered. These mecha- 83 C. It was also confirmed that stainless steel 316 L showed
nisms fall under three main categories: hydride-induced almost no influence from hydrogen over the entire tempera-
embrittlement (HIE); hydrogen-enhanced decohesion (HEDE); ture range investigated [10]. Studies are being actively con-
and hydrogen-enhanced localized plasticity (HELP). HIE is a ducted to increase the HER by coating metals such as stainless
known phenomenon in which HE is caused by hydrides steels 304 and 304 L, which are reported to undergo a reduc-
formed through a combination of specific elements (titanium. tion in their mechanical strengths under the influence of
zirconium, and vanadium) of alloys and hydrogen. Hydride hydrogen [11].
forms around the grain boundaries of exposed defects or Zinc and cadmium are representative of the coatings used
cracks. This is due to the fact that hydrogen diffuses into in studies, investigating the resistance of metals to HE, and are
places where stress is concentrated. Cleavage fractures arise reported to improve resistance [12,13]. Furthermore, studies
from the growth of hydrides with a brittle character. are being conducted to evaluate the influence of hydrogen on
HEDE is associated with local deformation facilitation new coating. Graphene-coated copper and nickel were
theory. When hydrogen permeates metals it can reduce the charged with hydrogen through a cathodic electrolytic
binding forces between the matrix atoms, and thus reduces method, thereby forming a HE environment with them. Sub-
energy required for the generation of cracks. Moreover, this sequently, by analyzing the amount of hydrogen charging and
phenomenon occurs more frequently at grain boundaries, performing a tensile test, it was reported that, for specimens
phase boundaries, or in areas of high dislocation density [5]. coated with graphene, the amount of hydrogen charging
HELP is also associated with local deformation facilitation significantly decreased, and that the mechanical strength
theory, and is a phenomenon in which the propagation of increased compared to uncoated specimens [14,15]. Addi-
initial damage is encouraged by hydrogen, through its ability tionally, the use of niobium as a coating to enhance HER was
of increasing dislocation mobility. The stress field of the reported [16].
dislocation is reduced by increasing the dislocation mobility, Among the materials known to react with hydrogen, pol-
and, as a result, crack propagation and destruction can occur ytetrafluoroethylene (PTFE) has been reported as effective
with relatively low external force [6]. A schematic of these hydrogen adsorption and desorption [17,18]; a schematic of
mechanisms is shown in Fig. 1. these processes is presented in Fig. 2. Depending on its
It is difficult to ascertain whether the overall phenomenon properties, PTFE absorbs a large amount of hydrogen. How-
of HE which is caused by a complex combination of the ever, it is understood that it also releases a large amount of
hydrogen environment and other conditions is caused by a hydrogen due to its excellent desorption properties, before the
specific mechanism. For this reason, it has not yet been re- hydrogen begins to affect the contiguous metal. As a result,
ported as a unified theory. However, in order to utilize the resistance of contiguous metal to HE should be improved.
hydrogen energy as a next-generation energy resource, studies However, no studies have been reported by which it is possible
aiming at the prevention of HE in metals and improvement of to evaluate the mechanical performance of PTFE in HE envi-
their resistance to embrittlement are attracting attention. In ronments, and thus prove these hypotheses.
particular, these studies have received the attention of the It is generally known that slow strain rates (SSRT) are ideal
shipbuilding industry, which is currently interested in mate- conditions for the diffusion of hydrogen, and are in accor-
rials that can withstand the cryogenic environment of liquefied dance with HE mechanisms. Therefore, a tensile test based on
hydrogen, for the development of liquefied hydrogen storage SSRT is generally used as a method of evaluating the perfor-
tanks or liquefied hydrogen fuel tanks. mance of materials subjected to HE environments [19].
international journal of hydrogen energy xxx (xxxx) xxx 3
Fig. 1 e Hydrogen embrittlement mechanisms: (a) Hydride-Induced Embrittlement (HIE); (b) Hydrogen-Enhanced
Decohesion (HEDE); and (c) Hydrogen-Enhanced Localized Plasticity (HELP).
Hydrogen affects the initiation and growth of initial cracks

[20], and fracture toughness is an important parameter for Materials and methods
evaluating a material's resistance to initial cracks [21].
Accordingly, fracture toughness is very important as a Material
parameter for evaluating a material's HER. The Charpy V-
notch (CVN) impact test is a method widely used to analyze Based on the characteristics detailed in the introduction,
fracture toughness [21,22]. Therefore, in order to prove the stainless steel 304 was selected as the material and was
hypothesis in this study, and propose a new way to improve fabricated according to Japanese standards. The composition
HER, the CVN impact test was carried out after PTFE coating of the stainless steel 304 used, is shown in Table 1. In this
had been applied to stainless steel 304 (known to be affected study, Teflon (manufactured by DuPont de Nemours, Inc.) was
by HE) under cryogenic conditions. The analysis conducted used as the PTFE. Table 2 shows the physical and chemical
included measurements of the hydrogen concentration, properties of PTFE.
electron back scatter diffraction (EBSD), and scanning electron
microscopy (SEM).
Specimens
The specimens used for the CVN impact test were manufac-
tured based on the ASTM E23-16 b: Standard Test Methods for
Notched Bar Impact Testing of Metallic Materials. The di-
mensions of these specimens were 55 mm 10 mm 10 mm
(length width thickness). The original specimens were
later coated with PTFE. First, to remove impurities in the
specimens and the coating liquid, cleaning was carried out.
Next, the processes of sanding (to enhance adhesion) and
preheating (to remove humidity) were performed. Finally,
spray coating was conducted, followed by heat treatment,
cooling (room temperature), and inspection (in the sequence
stated). After completion of these processes, the specimens
featured a coating 15e20 mm thick. Fig. 3 includes a photo-
Fig. 2 e Phenomena of adsorption and desorption in PTFE graph and the dimensions of an original and PTFE-coated V-
coating. notch specimen.
Table 1 e Composition of stainless steel 304.

Specimen no Chemical Elements (wt. %)
C Si S P Mn N Ni Cr Fe
304 0.05 0.5 0.002 0.021 1.05 0.05 8.04 18.24 Bal
for hydrogen pre-charging, and a constant current with a

Table 2 e Physical and chemical properties of PTFE.
current density range (0e20 A/m2) was supplied. Under these
Product code Property Data conditions, the hydrogen generated could diffuse into the
Vapor density of principal solvent 4.40 specimen surface. Fig. 4 illustrates the hydrogen pre-charging
(Air ¼ 1) system used for CVN impact test. According to the standard
Gallon weight (lbs/gal) 8.65 ISO 16573, a maximum charging time of 48e72 h is recom-
Specific gravity 1.04 mended; however, depending on the properties of the mate-
Percent volatile by volume 81.95
rial, the charging time can be extended. Preliminary CVN
958e313 Percent volatile by weight 72.89
Percent solids by volume 18.05
impact tests were conducted in the range (0e72 h) of hydrogen
Percent solids by weight 27.11 charging time at room temperature (RT).
VOC* less exempt (lbs/gal) 6.3 Fig. 5 illustrates the results of the preliminary CVN impact
VOC* as packaged (lbs/gal) 6.3 tests. The PTFE-coated specimens showed an unexpected
decrease in absorbed energy, compared to original specimens.
This was caused by aging degradation, which occurred
Electrochemical hydrogen pre-charging depending upon the exposure to the high-temperature envi-
ronment. Analysis of this phenomenon is provided from the
Hydrogen pre-charging was performed to analyze the tough- perspective of phase transformation in the results and dis-
ness of stainless steel 304 under HE conditions. The hydrogen cussion. The results of the preliminary CVN impact tests show
pre-charging method applied in this study is known as the
cathodic electrolytic method. The method is used globally,
because it is easy to set up and implement. The hydrogen pre-
charging method was conducted based on ISO 16573:2015:
SteeldMeasurement method for the evaluation of HE resis-
tance of high-strength steels. An electrolyte was required for
the generation of hydrogen, so an electrolyte solution
composed of 3% NaCl þ0.3% NH4SCN was used. It is known
that NaCl molecules react chemically in the H2O solvent and
generate Naþ and Cl ions, which act as electrolytes in the
solution, while NH4SCN prevents the Hþ ions from recom-
bining to H2 during hydrogen pre-charging [23]. According to
the ISO 16573, a specimen was connected to the cathode, and
a platinum mesh was connected to the anode. The current
supplied to generate hydrogen needs to be held constant; Fig. 4 e Schematic diagram of hydrogen pre-charging
therefore, a potentiostat model (WBCS3000 Standard Type system used for the CVN impact test.
Battery Cycler, WonATech, Seoul, Republic of Korea) was used
Fig. 3 e (a) Photograph and (b) Dimensions of a V-notched specimens (unit: mm).
at 196 C to meet the minimum design temperature

(165 C). This means that 196 C is essential for considering
the effects of occurrences impacts such as cryogenic liquid
cargo sloshing. However, 196 C is more suitable for evalu-
ating liquefied natural gas than liquefied hydrogen. Consid-
ering the experimental conditions that can be generated with
liquefied nitrogen, 196 C was applied as an experimental
scenario for evaluating validity for a cryogenic liquid cargo.
Table 3 illustrates the experimental scenario used in this
study. A cryogenic chamber was used to control temperatures
of 83 C and 196 C. For pre-cooling and thermal equilib-
rium, specimens were placed in the cryogenic chamber for 1 h.
According to the ASTM Standard Test Methods for Notched
Bar Impact Testing of Metallic Materials, when performing the
CVN Impact test under low temperatures and cryogenic con-
ditions, the test procedure should be performed within 5 s of
exposure to RT. Therefore, the CVN impact test was con-
ducted for each specimen less than 5 s after it was brought out
of the cryogenic chamber. To increase the reproducibility and
accuracy of the test results, five tests for each experimental
scenario were conducted.
Fig. 5 e Results of the preliminary CVN impact test at RT.
Measurement of hydrogen concentration
that the absorbed energy reduction rate had a maximum of
2.2% in the original specimens and a maximum of 3.9% in the After conducting hydrogen pre-charging under conditions 20
PTFE-coated specimen. However, these reduction rates ob- A/m2 over 0e15 days for the CVN impact test, measurement of
tained for different charging times were hard to see as being the hydrogen concentration was carried out using an analyzer
related to the phenomenon of HE. This is because when of inorganic material (ONH-2000, ELTRA GmbH, Haan, Ger-
hydrogen pre-charging was carried out in a short scenario many). To reduce errors, 3e5 samples (1 g each) were extracted
(maximum 72 h), the hydrogen concentration increased or from a cross-sectional area near the notch as soon as hydrogen
decreased based on specific time interval [24]. Therefore, the pre-charging was finished: 3e5 repeated measurements were
hydrogen pre-charging was conducted with a charging time of conducted. A graphite crucible was used in the furnace of the
0e15 days, and the current density was kept at 20 A/m2. The ONH-2000, and the sample was placed inside this graphite
amount of hydrogen diffusing into the specimens might be crucible. The crucible and the sample were completely melted
reduced by a decrease of electrolytes in the solution when the as the furnace was heated to 3000 C, and the hydrogen
hydrogen pre-charging test proceeds over a longer time captured in the sample was released in the form of atomic gas
period. This is because the electrical capacity applied is after reaction with the graphite at high temperature. The
influenced by the electrolyte concentration [25]. Therefore, hydrogen released (in the range 0.01e1000 mass ppm) was
during hydrogen pre-charging, the electrolyte solution was detected by a thermal sensing cell. Because the hydrogen
changed once every three days. concentration of samples extracted from the chosen sites can
be confirmed using the condition (high temperature) at which
CVN impact test metal samples can be melted, the ONH-2000 is used in a
After hydrogen pre-charging, the CVN impact test was con-

ducted using a Charpy impact machine (TM-CIMC500J, TEST
MATE, Gyeongnam, Republic of Korea). Using liquefied nitro- Table 3 e Experimental scenario used in this study.
gen, tests were conducted at three temperatures: RT, 83 C, Type Charging Current Charging Temperature of
and 196 C. The RT was applied as an experimental tem- Density (A/m2) Time CVN Impact Test
perature in consideration of the fact that residual hydrogen (days) ( C)
remains in the metals after hydrogen unloading. In the study Original 20 0 RT
reporting the largest decrease in mechanical performance of 3
stainless steel 304, 304 L, and 316 L, a temperature of 83 C Coated 9
was shown to have the largest effect on HE [10]. This indicates 15
Original 20 0 83
that 83 C is the temperature at which stainless steel 316 L is
3
most susceptible to HE. This is important because it is one of
Coated 9
the metals most resistant to HE. Based on this report, a tem- 15
perature of 83 C was applied as another experimental Original 20 0 196
temperature. According to the IGC Code (CCC 3) of the Inter- 3
national Maritime Organization (IMO) with regard to austen- Coated 6
itic steel for cryogenic service, an impact test was conducted 9
variety of studies related to hydrogen [26,27]. Fig. 6 illustrates

the system used to measure the hydrogen concentration.
Analysis of microstructure and crystallographic phase
In order to analyze the microstructure and crystallographic

phase, SEM and EBSD (based on SEM) were utilized. The
equipment used (for SEM and EBSD) included a Supra 25 and
Supra 40 (Carl Zeiss AG, Oberkochen, Germany). The SEM
analysis was used to determine the fracture mode according
to the influence of hydrogen and temperature, and was
focused on the absorbed energy properties involved in the
phase transition in EBSD. For clear SEM images, a processing
stage was performed to increase conductivity; fractured sur-
faces of specimens after CVN impact testing were coated with
platinum under the conditions of 10 mA for 80 s. EBSD analysis
requires grinding and polishing of the specimen. Before that, a
process by which the specimen was made into a uniform
shape using resin was performed (referred to as mounting).
Hot mounting was conducted using conductive Bakelite with
carbon filler. After specimens were hot mounted, their sur-
Fig. 7 e Graph of hydrogen concentration with type of
faces were ground with 400, 800, 1500, and 2400 grit sandpaper
specimens at 0, 3, 9 and 15 d of charging time (unit: mass
successively, then cleaned with acetone and dried immedi-
ppm).
ately. After that, a polishing process comprised of three steps
was conducted using polishing cloths. Whilst rotating the
polishing cloths in each step, diamond slurry (3 and 1 mm) and and raw data of the average hydrogen concentrations (the
colloidal silica suspension were sprayed. For analyzing EBSD, three samples were combined to reduce deviation) in relation
a hexagonal pixel with a step size of 0.2 mm was used. to the hydrogen charging time (0, 3, 9, and 15 days). It was
confirmed that hydrogen was detected even at 0 day for
hydrogen pre-charging specimens of all types. This was a
Results and discussion result of hydrogen formed through phenomena such as
summer moisture permeating a specimen and reacting with
Measurement of the hydrogen concentration the metal, or hydrogen already present since the
manufacturing of the metals. In the original and coated
The analysis focused on the relationship between the specimens, an increase in hydrogen concentration was
hydrogen concentration and hydrogen pre-charging time, and observed for 3 days during hydrogen pre-charging. From 3 d to
the results are as follows. Fig. 7 and Table 4 show the graphs 9 days of hydrogen pre-charging, a slight increase of hydrogen
Fig. 6 e Measurement system for the hydrogen concentration.
Table 4 e Raw data of the hydrogen concentration (unit:

mass ppm).
Type Hydrogen charging time (d)
0 3 9 15
Original 1.24 4.45 4.84 4.72
Coated 1.52 4.87 4.92 4.53
concentration in the original specimens was confirmed;

however, for the coated specimens, the increase in hydrogen
concentration was negligibly small. Irrespective of the char-
acteristics mentioned in the introduction for PTFE [17,18], a
similar behavior of hydrogen concentration was observed
between the original and coated specimens up until a specific
hydrogen pre-charging time (3 days). However, the afore-
mentioned characteristics (superb hydrogen adsorption and
desorption) of PTFE could be confirmed from 3 d to 9 days of
the hydrogen pre-charging. This indicates that the PTFE
characteristics appeared rapidly when a certain concentration
of hydrogen was charged. After 9 days, it was possible to
Fig. 8 e Graph of absorbed energy under different hydrogen
confirm that a decrease in the hydrogen concentration had
pre-charging times at RT, ¡83, and ¡196 C.
begun. This phenomenon was reported in a previous study
[24], and it could be confirmed that the hydrogen diffusion
proceeded toward the outside of a specimen after a certain concentration analysis, it was concluded that no large in-
period of time spend inside it. Overall, constant and similar fluences could be seen in the increase of hydrogen concen-
behaviors in the hydrogen concentrations of both the coated tration, and that the accumulated hydrogen concentration
and original specimens were confirmed in all time scenarios influenced the reduction of absorbed energy as time went on.
(0e15 days). Through these results, it was confirmed that the effect of
increasing hydrogen pre-charging time had little effect on the
CVN impact test PTFE-coated specimen. Comparing of results at 83 C and RT,
contrasting results appeared when hydrogen pre-charging
This analysis focused on the relationship between the absor- was carried out at 0 day. The difference in the absorbed en-
bed energy and the hydrogen pre-charging time and temper- ergy of the original and coated specimens became negligibly
ature; the results are as follows. Fig. 8 and Table 5 show the small, even if the reduction of absorbed energy caused by the
graphs and raw data for the average absorbed energy (three heat treatment during the coating process was considered.
samples were combined to reduce deviation) obtained from This phenomenon appeared according to differences in the
the CVN impact test, which was conducted under conditions thermal conductivity, and confirms the results of previous
of varying changing charging times (0, 3, 9, and 15 days) and studies, which stated the PTFE thermal conductivity was
temperature (RT, 83 C, and 196 C). lower than that of stainless steel 304 [28,29]. Thus, it seems
Fig. 9 shows the ratio of absorbed energy reduction ac- that the PTFE-coated specimens were less affected by low
cording to the change in the hydrogen pre-charging time. temperature than the original specimens. Among the three
From Fig. 8, it can be seem that the PTFE-coated specimens experimental temperatures, 83 C showed the largest
showed an unexpected decrease in absorbed energy change of absorbed energy behavior from the start of
compared to the original specimens, under conditions of 0 day hydrogen pre-charging. Moreover, reflecting the behavior of
of hydrogen pre-charging at RT. The difference of absorbed the hydrogen concentration after 9 days, the absorbed energy
energy can be accounted for by the change in the ratio of
austenite and martensite phases. The cause of this phenom-
enon was mentioned in a detail in the results of the EBSD
analysis. Regarding RT, it was confirmed that the absorbed Table 5 e Raw data of absorbed energy from CVN impact
energy behavior exhibits certain differences between the test (unit: J).
original and coated specimens. Fig. 9(a) shows the represen- Temperature ( C) Type Hydrogen charging time
tative results at ambient temperatures. As shown, the original (d)
and coated specimens showed a small decrease (<1%) until 3 0 3 9 15
days. However, after that, different behaviors were seen; the RT Original 355 353 J 330 316
coated specimens maintained a small reduction until 15 days, Coated 294 294 J 290 283
when they finally showed a decrease of <5% in absorbed en- 83 Original 259 223 J 204 216
ergy. However, in the case of the original specimen, the Coated 255 239 J 216 231
reduction of absorbed energy sharply increased from 3 to 9 196 Original 183 158 J 155 153
Coated 195 168 J 162 162
days. Comparing these results with those of the hydrogen
Fig. 9 e Ratio of reduction of absorbed energy according to changing hydrogen pre-charging time at (a) RT, (b) ¡83 C, and (c)
¡196 C.
after 9 days increased for both original and coated specimens. not greatly affect the absorbed energy, and only at cryogenic
This suggests that the original and coated specimens were temperatures were the effects valid. When hydrogen perme-
very sensitive to the hydrogen concentration and hydrogen ates metals that are exposed to hydrogen environments,
pre-charging time at 83 C. Despite these results, the baking can force the hydrogen to leave them [30]. Thus, baking
decrease in the absorbed energy for the coated specimens was is considered as one of various methods for preventing HE and
lower than for the original specimens. Looking at the results improving HER. In the case of AISI 4340, baking had no sig-
for 196 C and 0 d of hydrogen pre-charging, it can be nificant effect upon the hydrogen released from steel speci-
confirmed that the absorbed energy of the coated specimens mens. Moreover, when increasing baking temperature, it was
was higher than that of the original specimens, in contrast to confirmed that the Charpy impact energy of hydrogen charged
what was seen for RT and 83 C. This means that the insu- specimens was lower than uncharged specimens [31]. This
lation performance according to thermal conductivity was means that the effects of preventing HE by hydrogen expul-
reflected more notably at cryogenic temperatures. After that, sion through baking vary according to the type of metal and
these results were maintained, and the absorbed energy baking temperatures. In addition, the need for periodic baking
sharply decreased until 3 days. Furthermore, the ratio of before the permeating hydrogen affects the metal can
reduction for absorbed energy at all charging times was constitute a limit. Contrary to previous studies, the PTFE
similar between the original and coated specimens. This coating showed excellent HER, even in long-term hydrogen
means that the hydrogen pre-charging time (after 3 days) did exposure.
Electron back scatter diffraction (EBSD)
This analysis looked at the reason for the initial decrease of

absorbed energy that occurred with a PTFE coating, and the
results are as follows. Fig. 10 shows images of the EBSD
analysis in specimens for which the CVN impact test had not
been conducted. Trace amounts of martensite were discov-
ered in the original specimens, though stainless steel 304 is
known to be austenite. This phenomenon was caused by
cutting stresses during the process of manufacturing the
specimens, or during the process of extracting samples for the
hydrogen concentration measurement. In spite of this, the
martensite ratio of the coated specimens was higher than for Fig. 11 e EBSD images of specimens after CVN impact
the original, and this phenomenon was caused by heat testing under the conditions of RT and 0 d of hydrogen pre-
treatment during the coating process, which transformed the charging for: (a) original specimens, and (b) coated
stainless steel 304 from austenite into a two-phase structure, specimens.
containing both austenite and martensite [32].
Fig. 11 shows the EBSD analysis of the CVN impact test
conducted at RT for the original and coated specimens on
Scanning electron microscopy (SEM)
0 day of hydrogen pre-charging. A higher ratio of martensite
could be confirmed in both the original and coated specimens
This analysis looked at the changing fracture mode according
than in specimens for which the CVN impact test had not been
to temperature and the hydrogen pre-charging time; the re-
conducted. This is known as stress-induced martensitic sults are as follows. HE caused by the penetration of hydrogen
transformation [33,34], and is a phenomenon by which has been reported to cause a cleavage structure, which in-
austenite in stainless steel 304 is transformed into martensite dicates the brittleness of steel [37]. Generally, cleavage struc-
by the Charpy impact energy. Even considering the generation tures have the features of a delamination shape, and dimple
of martensite through absorbed energy, the ratio of structures have the features of a microvoid shape [38]. SEM
martensite in the PTFE-coated specimens was higher than in
analysis was conducted based on these characteristics. Fig. 12
the original specimen. This phenomenon corresponds with
shows SEM images after the CVN impact test had been con-
the results mentioned earlier and was caused by the heat
ducted, at RT. For these conditions, dimple shapes such as
treatment. The metal toughness decreases when the propor-
those found in ductility fractures were confirmed in both the
tion of martensite, which is known to have a brittle structure,
original and coated specimens up until 3 days of the hydrogen
is increased [35]. Through these results, the initial decrease of
pre-charging. After that, it was possible to confirm a differ-
absorbed energy for the PTFE-coated specimens on 0 day of ence in the fracture modes of the original and coated speci-
hydrogen pre-charging can be accounted for. Generally, it was mens. With the coated specimen, ductility fractures of the
reported that the formation of martensite increases the same dimple shape were present in the other scenarios after 3
hydrogen diffusivity in the austenitic stainless steels, and the days; however, in the original specimen, cleavage shapes such
increase in hydrogen diffusivity accelerate HE [36]. However, as those found in brittle fractures were confirmed. A mixed
based on the CVN impact test results of the coated specimens mode of dimple and cleavage shapes showed at 9 days, while
at RT, it cannot be determined whether heat treatment
the cleavage shape only showed at 15 days. These changes of
accelerate HE.
fracture mode are caused by the influence of hydrogen, and
confirm that the fracture mode corresponds to the CVN
impact test result.
Fig. 13 shows the SEM images after the CVN impact test at
83 C. For these conditions, the fracture mode according to
hydrogen pre-charging time showed the same results for both
the original and coated specimens. The fact that temperature
promotes brittleness was confirmed by the cleavage shape
that appeared at 0 day. Through images take 3 days later, it
was confirmed that both the low temperature and hydrogen
affect the fracture mode when compared with the impact test
results.
Fig. 14 shows the SEM analysis images after the CVN
impact test at 196 C. For this condition, only the cleavage
shapes showed, regardless of PTFE coating. These results were
Fig. 10 e EBSD images of specimens for which the CVN caused by the cryogenic temperature (196 C) at which
impact testing was not carried out: (a) Original specimen, stainless steel 304 becomes brittle [39]. By comparing the re-
and (b) Coated specimen. sults of the CVN impact tests, it was confirmed that cryogenic
temperature has a greater effect than hydrogen.
Fig. 12 e SEM images of fracture surface after CVN impact testing at RT: original (a) 0, (b) 3, (c) 9, (d) 15 d and coated (e) 0, (f) 3,
(g) 9, (h) 15 d.
Fig. 13 e SEM images of fracture surface after CVN impact testing at ¡83 C: original (a) 0, (b) 3, (c) 9, (d) 15 d and coated (e) 0,
(f) 3, (g) 9, (h) 15 d.
Fig. 14 e SEM images of fracture surface after CVN impact testing at ¡196 C: original (a), (b) 3, (c) 9, (d) 15 d and coated (e) 0, (f)
3, (g) 9, (h) 15 d.
shows that the absorbed energy is more affected by tem-

Conclusions perature than by the hydrogen concentration and
hydrogen pre-charging time.
In summary, to enhance the HER of stainless steel 304 and to As a result of the EBSD analysis, it became clear that three
prove the hypothesis presented in this study, CVN impact elements affect phase changes: stresses due to processing,
testing was carried out on stainless steel 304 with PTFE heat treatment during the coating process, and the Charpy
coating under a HE environment. The main conclusions are as impact energy. It was also confirmed that these elements
follows: also affect the metal's toughness.
From hydrogen concentration measurement, very similar PTFE coating, which exhibits excellent HER can be an
hydrogen adsorption and desorption behaviors were attractive candidate in applications for hydrogen containment
confirmed regardless of the PTFE coating used. This result systems under i) extreme thermal cycles due to loading, and
indicates that the properties of PTFE do not affect the unloading of hydrogen, and ii) hydrogen exposure in long term
hydrogen concentration. on operations.
In conditions of RT, though there was an initial decrease of
absorbed energy in the coated specimens at 0 day of
hydrogen pre-charging, the absorbed energy reduction rate
until 15 days of the coated specimens was confirmed as Acknowledgements
3.7%, much lower than the 11% of the original specimens.
This indicates that the PTFE coating improves HER. This work was supported by the R&D Platform Establishment
In conditions of 83 C the absorbed energy reduction rate of Eco-Friendly Hydrogen Propulsion Ship Program (No.
until 15 days of the coated specimens was confirmed to be 20006644) funded by the Ministry of Trade, Industry & Energy
9.4%, lower than the 16.6% of the original specimens. This (MOTIE, Korea). This work was supported by the National
cannot be compared with the performance at RT, because Research Foundation of Korea (NRF) grant funded by the
the absorbed energy reduction rate at this temperature was Ministry of Science and ICT (MSIT) (No. 2018R1A2B6007403).
too small. However, it can be confirmed that PTFE coating
enhances HER, compared with non-coated samples
In conditions of 196 C, it was confirmed through the re- references
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international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Effect of PTFE coating on enhancing hydrogen

Jae-Sik Hwang, Jeong-Hyeon Kim, Seul-Kee Kim, Jae-Myung Lee*

highlights graphical abstract

The effects of polytetrafluoro-

article info abstract

Article history: The phenomenon of hydrogen embrittlement phenomenon is known to be a major

Austenitic stainless steels of the 300 Series have excellent

Hydrogen affects the initiation and growth of initial cracks

Table 1 e Composition of stainless steel 304.

for hydrogen pre-charging, and a constant current with a

at 196 C to meet the minimum design temperature

After hydrogen pre-charging, the CVN impact test was con-

variety of studies related to hydrogen [26,27]. Fig. 6 illustrates

Analysis of microstructure and crystallographic phase

In order to analyze the microstructure and crystallographic

Fig. 6 e Measurement system for the hydrogen concentration.

Table 4 e Raw data of the hydrogen concentration (unit:

concentration in the original specimens was confirmed;

Electron back scatter diffraction (EBSD)

This analysis looked at the reason for the initial decrease of

shows that the absorbed energy is more affected by tem-

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