metals

Article
Evaluation of Welded Joints in P91 Steel under
Different Heat-Treatment Conditions
Francisco José Gomes Silva 1,2, * , António Pedro Pinho 1 , António Bastos Pereira 2 and
Olga Coutinho Paiva 1
1 ISEP—School of Engineering, Polytechnic of Porto, 4200-072 Porto, Portugal; [email protected] (A.P.P.);
[email protected] (O.C.P.)
2 TEMA—Centre for Mechanical Technology and Automation, Department of Mechanical Engineering,
University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal; [email protected]
* Correspondence: [email protected]; Tel.: +351-228340500




Received: 18 December 2019; Accepted: 7 January 2020; Published: 8 January 2020


Abstract: P91 steel has been of interest to many researchers over the past two decades. This interest
is because this steel has very interesting characteristics for application in power plants, where it is
common to have pipes that need to support steam at temperatures between 570 and 600 ◦ C, and at
pressures in the range of 170 to 230 bar. These working conditions are quite severe for most common
steels, requiring increased high-temperature mechanical strength as well as high creep resistance.
The manufacture of these pipes normally includes welding operations, which must preserve the
main characteristics of this type of steel. This justifies the concern of the researchers to ensure the
best welding conditions so that the preservation of the properties of these steels becomes possible.
The present work intends to depict the best results obtained varying the heat-treatment conditions
applied to weldments made on heat-resistant steel P91. This steel usually takes the designation
SA 213 T91 (seamless tube) or SA 335 P91 (seamless pipe), according to ASME II, as well as the
designation X10CrMOVNb9-1 according to EN 10216-2. The purpose of this study is to compare the
behavior of pipe welding under different post-welding heat-treatment (PWHT) conditions. One of
them is performed with thermal cycles (preheating, post-heating, and the post-weld heat treatment)
in agreement with most construction codes and standard rules. The second one is performed without
any thermal cycle before and after welding. Both welds were made by the same process, TIG
(Tungsten Inert Gas, or GTAW—Gas Tungsten Arc Welding) in the horizontal position (2G according
to ASME IX) and the same welding parameters. In order to evaluate the results obtained in the
welds, microstructure analyses, hardness measurements, bending tests, and tensile tests at room and
high temperature (600 ◦ C) have been performed. Other tests were also carried out according to the
quality procedures, such as visual, penetrant dye, and X-ray tests. Regarding the different strategies
used in the heat treatments, the best results have been obtained using a strategy similar to the one
currently in use and recommended by construction codes and steel manufacturers but excluding the
phases’ transformation time, and it was possible to observe that the tensile strength is impaired by
about 2% to 9% at room and elevated temperatures, respectively; the elongation is reduced by 39% at
room temperature but keeps a good performance at elevated temperature; the hardness profile is
very similar at both temperatures; the microstructure presented is compatible with the requirements;
and no cracking trend has been reported. Thus, a new strategy for the welding heat treatment of
grade 91 steels was drawn, saving energy and processing time.

Keywords: P91 steel; heat-resistant steels; welding; heat treatment; PWHT; welds characterization;
microstructures; tensile strength; hardness; heat-treatment processing time; sustainability

Metals 2020, 10, 99; doi:10.3390/met10010099 www.mdpi.com/journal/metals

Metals 2020, 10, 99 2 of 23

1. Introduction
Grade 91 steel was developed based on steels that emerged in the 1960s with typically 12% Cr
content. The development of grade 91 was mainly due to creep problems, as 12% Cr steels traditionally
failed when exposed to prolonged creep conditions such as those in power plants where these steels
were used, exposing them to high pressures and temperatures of around 565 ◦ C. Thus, steels with
increased creep resistance have emerged. Grade 91 was originally developed by Oak Ridge National
Laboratory in Tennessee, USA, typically consisting of 9% Cr and 1% Mo, which were initially called P9
steel presented as its main focus use in power plants [1]. Subsequently, this steel was studied and its
composition was evolved through the addition of other elements, such as vanadium and Nb, and with
controlled N content, thus giving rise to 91 steel grade. This new grade of steel substituted the P22
steel grade and can assume various designations, unfolding under designations such as SA 213 P91
(seamless tube) and SA 335 P1 (seamless pipe) according to ASTM, or X10CrMoVNb9-1 according to
BS EN 10216-2 [2]. The P91 steel grade also responded to the demand for the increased efficiency of
power plants, which now need to operate at higher temperatures in order to release lower amounts of
CO2 for the same volume of energy generated. Indeed, the latest composition of the P91 steel grade
allows continuous working at temperatures in the range of 600 ◦ C without being affected by creep
phenomena, even under elevated stress conditions. Since welding of the various components that
form part of the power plants is required, P91 steel has been the subject of numerous studies, most of
which are briefly described below. The excellent properties of P91 steel also come from the careful
distribution of fine Nb and V carbonitrides, which have a microstructure that can be changed during
the welding process [3].
Several researchers have devoted their attention to the characterization of P91 steel welds made
using different processes. In a recent study, Vidyarthy and Dwivedi [4] compared the use of TIG and
A-TIG (Activated Flux TIG) processes (GTAW) on P91 steel welds, investigating the influence of CeO2
and MoO3 -based activating flux on some factors that strongly condition welding, such as such as
heat input, weld bead geometry, and angular distortion during single-pass execution. The use of
A-TIG aims to overcome the productivity limitations imposed by the conventional TIG process, which
is essentially geared to small thicknesses. The thin activated flow layer used in the A-TIG process
substantially improves the process productivity [5]. Welding beads performed by both processes
were also investigated, analyzing the resulting microstructure, mechanical strength, microhardness,
and impact strength (Charpy). It was observed that for the same set of parameters used in both welding
processes, the A-TIG process promoted an increase in the heat input transmitted to the joint due to the
action of the activating fluxes, which resulted in an increase of 200% in the joint penetration when
CeO2 flux is used, and 300% when MoO3 flux is used, compared to the conventional TIG process.
In the analysis of welded joints, other benefits were also observed, such as less angular distortion,
which dropped from 1.96◦ in conventional TIG welding to 0.78◦ using CeO2 flux or 0.12◦ when using
MoO3 flux. The microstructure was predominantly dominated by martensite in the welding zone,
and coarse precipitates such as M23 C6 carbides were also observed in the primary austenite grain
boundaries. The ultimate tensile strength (UTS) in welded samples increased by 2% related to the
parent metal, and the microhardness increased as well. Conversely, impact resistance decreased in the
A-TIG process compared to the conventional TIG process. Dhandha and Bandheka [5] also studied the
A-TIG process applied to P91 steel using as fluxes Fe2 O3 , ZnO, MnO2 , and CrO3 . These authors also
confirmed that penetration is always improved at least 100% using these kind of activated fluxes in
that process, and a decrease in bead width was observed as well, as usually required. The best results
were achieved using ZnO activated flux. The surface appearance/morphology of the weldments was
considered as very good.
Marzocca et al. [3] studied P91 steel welds performed by means of the flux cored arc welding
(FCAW) process, using two different rutilic filler metals (E91T1 and E91T1-G) and 80% Ar/20% CO2
shielding gas. The main focus of that work was to study the resulting microstructure of the welded
zone, using five welding passes to fill up the chamfer previously prepared and a heat input energy
Metals 2020, 10, 99 3 of 23

of 1.5 kJ/mm. M23 C6 carbides were found in all zones, i.e., the parent metal (PM), fused zone (FZ),
and heat-affected zone (HAZ). VN (Vanadium-based) precipitates were also observed in all zones
but with a decreased size and greater dispersion. However, NbCN was only found in the PM and
HAZ. In addition, trying to overcome the lack of productivity characteristic of the conventional TIG
process, Krishnan et al. [6] used the pulsed gas arc welding (GMAW-P) process using a cored wire
filler material to weld 12 mm thick P91 steel sheets in a single pass. The authors reported that the best
welding results were obtained using 75◦ bevel aperture and 1.38 kJ/mm heat input, which corresponds
to a welding speed of 320 mm/min and a current intensity of 270 A. Very interesting properties of
mechanical strength (UTS = 812–849 MPa) and the impact strength of the weld bead (104–127 J) have
also been reported. The deposition rate with flux cored wire was increased by about 42% compared to
the use of a common solid wire, considering the same set of parameters and welding conditions. Other
authors using the same process reported a significant decrease in the defects generated during the
welding process, namely spatter, welding porosity, and lack of fusion decreasing, as well the weld
width [7,8]. Other processes such as shielded metal arc welding (SMAW), submerged arc welding
(SAW), and flux cored arc welding (FCAW) have also been tested to maximize the welding efficiency
of P91 steels, but non-metallic inclusions have been observed in the weld beads, loss of toughness, and
excessively high oxygen content in the welds, considering the studies conducted during the 2000–2009
decade [9,10]. However, a further study developed by Arivazhagan and Kamaraj [11] in 2015 is in line
with other works published more recently, which reported a very low amount of fine microinclusions
less than 2 µm in size, allowing toughness values around 47 J. However, this value can be improved by
15%–25% using 100% Argon instead 80% Ar/20% CO2 . An increase in the post-welding heat-treatment
(PWHT) duration at 760 ◦ C from 2 to 5 h has been reported as the main factor behind the 30% to 50%
toughness improvement in welded joints.
Shanmugarajan et al. [12] used an autogenous laser beam in P91 steel welding but reported the
presence of the delta ferrite phase in the weld beads, which was attributed to the amount of heat
given to the joint. Kundu et al. [13] used an electron beam to weld P91 steel, but too high residual
stresses were observed in welding of thicker thicknesses. In order to increase the efficiency in the
GTAW process, Pai et al. [14] reached an increased filler metal deposition rate using it in preheated
conditions, but in contrast, they observed a significant decrease in the joint toughness, which was
attributed to the excessive heat passed to the joint in the process.
One of the main problems that has been worrying researchers is the possible drop in toughness
and creep behavior due to the welding process. This has motivated several studies. El-Dosoky et al. [15]
investigated the behavior of welded joints subjected to prolonged exposure at 600 ◦ C under 120 MPa
and 70 MPa loads, verifying that the creep resistance is conditioned by the fine grain of the heat-affected
zone (FGHAZ). It has also been reported that welded samples have a higher creep rate than the parent
metal mainly in the tertiary region, and that creep begins earlier in welded samples relative to the parent
metal for the same load applied at 600 ◦ C. Hyde et al. [16] studied the crack growth in welded P91 steel
samples by creep crack growth tests at 650 ◦ C, using compact strain (CT) test specimens, comparing the
results obtained experimentally with simulations performed by the finite element method (FEM). The
authors also confirmed a good correlation between the creep crack growth rates in the P91 parent metal
and the cross-weld specimens for a given contour-integral (C*) [17], in which the crack growth rate was
10 times higher in the cross-welded CT specimens than those of the parent metal. Using the same type
of specimens, Kumar et al. [18] reported similar conclusions, adding the idea that the HAZ enables the
faster generation and growth of cracks to the detriment of the parent material and melted zone, creating
the best conditions for the deviation of crack paths from those zones to the HAZ. In addition, using
CT specimens of P91 steel welded and non-welded, Venugopol et al. [19] reached similar conclusions,
using the fracture mechanics parameter C*. The conclusion drawn by these researchers, which was
later confirmed by other works already cited here, emphasized that the creep crack growth rate is
higher at the HAZ, which is especially true when lower C* values are reported. A similar study was
recently conducted by Baral et al. [20], using non-welded P91 steel samples and welded samples of the
Metals 2020, 10, 99 4 of 23

same material, in a temperature range between 600 and 650 ◦ C, and loads between 50 and 180 MPa.
The observations made by these authors allowed ratifying the previous opinion of other researchers,
in which the influence of the Cr23 C6 coarse grains in the HAZ intercritical zone is clear, significantly
conditioning the creep resistance, and that the minimum creep rate clearly follows Norton’s power
law. Trying to minimize the HAZ width, Divya et al. [21] carried out a comparative study between the
laser welding (LW) of P91 steel welding, which leaves a HAZ of about 1 mm, with shielded metal arc
welding (SMAW), which leaves a HAZ of about of 2.5 mm. The study was conducted to study the
failure under creep conditions in the HAZ, which is commonly known as Type IV cracking. It was
found that the microstructural damage induced by the LW is lower than in the case of the SMAW
process. Although the width of the HAZ was effectively smaller in the case of LW, all specimens
failed in the intercritical region of the HAZ. This shows that there is no benefit brought by LW in this
case, because no significant improvements are brought to the Type IV cracking resistance. Wang et
al. [22] performed PWHT at different temperatures on P91 welds, noting that there is a transition from
Type IV cracking to Type I cracking in the HAZ intercritical region when moving from 600 to 840 ◦ C
treatment temperatures. In fact, the authors emphasize the idea that it is impossible to eliminate the
HAZ intercritical region by PWHT if the temperature at which this treatment is performed does not
exceed the Ac1 critical temperature of the parent metal. The intercritical structure formed on the basis
of transformed austenite grains and untransformed ferrite grains in the fused zone may be the source
of creep failure, i.e., Type IV cracking. These conclusions emphasize the importance of the temperature
at which the PWHT must be conducted. Thus, PWHT conditions deserve special attention.
Sharma et al. [23] recently studied the effect of PWHT on welded P91 steel, reporting that the
best conditions encountered to maximize the mechanical strength of welded pipe would be a 2 h
treatment at 760 ◦ C. In this study, the TIG process with heated wire was used, which allowed a smaller
heat passage to the welded joint, minimizing the HAZ. In 2014, Venkata et al. [24] reported that the
maximum temperature at which a PWHT should be performed is 770 ◦ C and should always be lower
than the austenite starting temperature (Ac1 ). In a study conducted in 2012 by Paddea et al. [25],
the highest residual stresses (600 MPa) have been reported to be located near the outer boundary
of the HAZ and toward the weld root in both PWHT and as-welded samples. As a result of these
residual stresses, premature Type IV creep failures were observed in these 9–12% Cr (P92) steel welds.
However, after PWHT, the residual stresses dropped to values around 50 MPa in the vicinity of the
HAZ. Regardless of PWHT, the region where the highest level of residual stresses was measured has
always been HAZ’s intercritical region, which is the most vulnerable to Type IV cracking phenomena.
Pandey et al. [26] performed creep tests at a temperature of 620 ◦ C and loaded in the range of 150
to 200 MPa in multi-pass welded samples in P91 steel both in an as-welded condition and subjected
to a set of heat treatments after welding. This set of treatments consisted of keeping the samples at
760 ◦ C for 2 h with subsequent air cooling, followed by a re-austenitization treatment at 1040 ◦ C for
1 h, and then further tempering at 760 ◦ C again for 2 h, with a new air cooling process. It was reported
by the authors that this treatment substantially increased the creep life of the samples, especially
for a 150 MPa load. Laves phases have also been reported, as well as the change in the preferred
failure location which, when in the as-welded condition, was caused by Type IV cracking in the HAZ
intercritical region, but when subjected to the latter treatment, the breaking zone happened in the base
material because the treatment conveniently unifies the structure along the samples. The same results
are also reported by some of the same authors in [27]. Similar experiments carried out by a similar
team of authors but using multi-pass shielded arc welded metal (SMAW) in P91 steel butt joints on
18 mm thick plate samples, which showed that the hydrogen taken to the joint in the welding process
(6.21 mL/100 g) gave rise to hydrogen embrittlement, which is a situation that cannot be overcome
by the sequence of treatments performed (identical to that described above). However, without such
a large content of hydrogen present, the treatment produces a clear uniformity of the microstructure in
the welded samples [28].
Metals 2020, 10, 99 5 of 23

Several studies focusing on welding P91 steel with other materials, i.e., dissimilar joint, including
P92 steel [29], PM2000 steel [30], AISI 304 stainless steel [31], and IASI 316L stainless steel [32], have
also been carried out. The results are promising and some of the problems reported above when using
P91/P91 joints seem to tend to be softened, depending on the welding process and conditions used.
Studies in recent years reveal how important it is to know how to properly weld and treat P91 steel
welds. Thus, this work aims to deepen the previous studies by performing different PWHT cycles to
welded P91 steel samples, analyzing the resulting microstructure, mechanical strength, and hardness.

2. Materials and Methods

2.1. Materials
In order to carry out the experimental work, a pipe with Ø48.3 mm and a thickness of 5 mm
in SA 355 P91 steel provided by Vallourec Brazil (Belo Horizonte, Brazil) was selected. Its chemical
composition and main mechanical properties provided by the supplier can be seen in Tables 1 and 2,
respectively. The length of each sample was 150 mm, and the preparation (chamfer) was made in
just one tip of the pipe. The preparation details can be seen in Table 3. Twenty-five samples have
been produced under each set of conditions, in order to provide at least five samples for each kind of
destructive test. The results of the tests carried out in this work present the average value followed by
the standard deviation.

Table 1. Chemical composition of the parent metal SA 355 P91.

C Si Mn P S Al Cr Ni Mo V Cu W Nb N
0.100 0.290 0.500 0.017 0.001 0.009 8.600 0.170 0.980 0.230 0.120 0.030 0.080 0.052

Table 2. Main mechanical properties of the parent metal SA 355 P91 (Data from Vallourec company).

Rp0.2 (20 ◦ C) Rm (20 ◦ C) Elong. (20 ◦ C) Rp0.2 (600 ◦ C) Rm (600 ◦ C) Hardness

521 MPa 693 MPa 25.2% 320 MPa 365 MPa 221 HV30

Table 3. Chemical composition of the filler metal ER90S-B9.

C Si Mn P S Cr Ni Mo V Cu
0.095 0.235 0.545 0.007 0.003 8.980 0.545 0.910 0.210 0.125

As filler metal, wire with Ø2 mm with the reference ER90S-B9 was used, which was provided
by Electro Portugal, Lda. (Porto, Portugal); its chemical composition can be observed in Table 3.
The mechanical properties of this filler metal follow the EN10204 standard. This filler metal was
selected because it is recommended by the ASME manufacturing code for P91 steel.

2.2. Methods
Since the main objective of this work is to analyze the influence of different heat treatment cycles
on P91 steel welded joints, the welding conditions were kept constant for producing the samples.
Initially, the pipes were cut in a circular sawing machine Kaltenbach KKS 450 S, and the chamfer
was performed in a conventional lathe Knuth V-Turn Pro (KNUTH Werkzeugmaschinen GmbH,
Wasbek, Germany). After that, the samples were properly cleaned, avoiding the presence of chips. The
welding process used in this work was GTAW in the position of 2G using a Kemppi (Kemppi, Lahti,
Finland) Master TIG MLS 4000 multi-process power source welding machine. To perform the welding,
the samples were properly aligned, and thermocouples were attached to the surface close to the weld
joint. Following Kobelko’s recommendation for this type of material (between 0.8 and 1.6 kJ/mm),
a thermal delivery of 1.33 kJ/mm was selected, which conditioned the welding parameters. Good
Metals 2020, 10, 99 6 of 23

engineering practice recommends that a current rating of about 45 A per each millimeter diameter of
the filler material should be used. Thus, a current intensity of 95 A was selected, as the diameter of the
wire used as the filler metal was ±2 mm. The main parameters used in the welding process are shown
in Table 4.

Table 4. Main parameters used in the welding process.

Parameter Value Parameter Value

Process GTAW Current/Polarity DC (Direct polarity)
Shielding gas 100% Ar+ Current intensity 95 A
Gas flow 14 L/min Voltage 14 V
Welding position 2G Traveling speed 42 mm/min
Chamfer type V Thermal input 1.33 kJ/mm
Chamfer angle 60◦ Filler metal diameter 2 mm
Root opening 3 mm Tungsten electrode Ø2.4 mm (EWCE-2)
Root face 1 mm Number of passes 2

The voltage was adjusted automatically, following the characteristic curve of the welding machine.
After the welder obtained the current intensity, the voltage, and the range of thermal delivery, the
traveling speed was adjusted, taking into account the welding position and the thickness of the pipe
to be welded. For calculating the traveling speed, the following expression for the thermal delivery
was used:
U×I
 
Q = k× × 10−3 (1)
v
where Q is the thermal delivery (kJ/mm), k is the thermal efficiency factor, U is the arc voltage (V), I is
the current intensity (A), and v is the traveling speed (mm/s). This is valid for the first pass, because it
is well known that for the second pass, a higher level of current can be used (+10%), as well as a lower
traveling speed (−20%), in order to properly fulfill the chamfer. These new parameters for the second
pass will result in higher thermal delivery, although it is controlled in order to prevent the appearance
of welding defects.
For preheating, post-heating, and PWHT processes, a Weldotherm (Weldotherm, Essen, Germany)
VAS 82-12 Digit 1000 Heat Treating Unit provided with 12-channel capacity was used, with six channels
that were capable of using electrical resistances up to 135 A and another six channels that were capable
of using electrical resistances up to 90 A.
Different thermal cycles have been applied to the welded samples in order to study the mechanical
behavior of the joints. In Figure 1, it is possible to observe the different cycles selected, as well as the
code used in this work, making the correlation with the subsequent analyses easier. Table 5 presents
the main levels of temperature used in each set of heat treatments. The main argumentation behind the
selection of the different thermal cycles imposed to the samples used in this study can be found below:
• P_APP_T00: these samples were used in the basic condition, i.e., without any kind of pre- or
post-treatment. Although it is well known that this condition does not present the best conditions
to be used in practice, it can be useful to know what happens when the best practices are not
applied and compare the results with the other sets of heat treatment applied to the other sets
of samples;
• P_APP_T01: the procedure used in this set of samples followed the rules recommended by the
construction codes, standards, and some important manufacturers. This procedure uses all the
advantageous settings and is considered as ideal for this kind of base material. The complete
procedure includes preheating, welding, post-heating, transformation time, and finally, PWHT. Its
main disadvantages are the long processing time as well as the energy consumed; furthermore, it
is not environmentally friendly or productive;
• P_APP_T02: this batch of samples has been produced to verify the influence of hydrogen (if inserted
into the weld), and how it interferes with bonding, along with residual stresses in the weld and
Metals 2020, 10, 99 7 of 23

corrosion phenomena. In order to simulate this situation, preheating was used, but without
post-heating treatment. At the end of the welding process, the samples have been protected with
a ceramic fiber blanket, avoiding a fast cooling process until it reached room temperature. No
phases’ transformation time was used. The PWHT was applied just six months later;
• P_APP_T03: the purpose of the selection of these conditions is the same as that for P_APP_T02 but,
in thisMetals
case, a post-welding treatment was performed in order to eliminate any possible
2020, 10, x FOR PEER REVIEW 7 of 24
retained
hydrogen. It is intended to compare this situation with the previous one, analyzing the effect of
• P_APP_T03:
the post-welding the purpose of the selection of these conditions is the same as that for P_APP_T02
treatment;
but, in this case, a post-welding treatment was performed in order to eliminate any possible
• P_APP-T08: the conditions used in this set of parameters are very similar with those of the
retained hydrogen. It is intended to compare this situation with the previous one, analyzing the
P-APP_T01 setofbut,
effect in this case,
the post-welding the time of transformation was changed. After cooling to room
treatment;
•
temperature, the samples
P_APP-T08: have been
the conditions used insubjected immediately
this set of parameters to PWHT.
are very Thethose
similar with main of purpose
the P- of this
APP_T01 set but, in this case, the
procedure is to save energy and time in the process. time of transformation was changed. After cooling to room
temperature, the samples have been subjected immediately to PWHT. The main purpose of this
procedure is to save energy and time in the process.
Sample
Set of thermal cycles
reference

P_APP_T00

P_APP_T01

P_APP_T02

P_APP_T03

Figure 1. Cont.
Metals 2020, 10, 99 8 of 23

Metals 2020, 10, x FOR PEER REVIEW 8 of 24

P_APP_T08

Figure 1. Different sets of thermal cycles used for each set of samples utilized in this work. Legend: (a)
Figure 1. Different sets of thermal cycles used for each set of samples utilized in this work. Legend:
Pre-heating; (b) Welding; (c) Post-heating; (d) Transformation time; (e) Controlled cooling; (f) Post-
(a) Pre-heating; (b) Welding;(PWHT).
welding heat-treatment (c) Post-heating; (d) Transformation time; (e) Controlled cooling;
(f) Post-welding heat-treatment (PWHT).
Table 5. Different thermal cycles applied to the P91 samples.
Table 5. Different thermal cycles applied to the P91 samples.
Pre-Heating and Global PWHT Localized PWHT
Heatin Time PWHT
Pre-Heating and Global Heatin Time
Localized Coolin
PWHT
Cooling Tempe
Sample g Tempe
Time After Tempe g Tempe AfterTime g
Heating Cooling Time Heating Cooling -
Code Temperature -Rature
Sample Code After Weldin Temperature
-RatureTime Temperature
-Rature Weldi After Temperature
Rate Rate Rate Rate Rature
Rate Welding Rate
g Rate ng Welding Rate
(◦ C/h) (◦ C) (min) (◦ C/h) (◦ C) (min) ◦
(min ( C/h) (◦ C) (min) (◦ C/h) (◦ C)
(°C/h) (°C) (min) (°C/h) (°C) (°C/h) (°C) (min) (°C/h) (°C)
P_APP_T00 As-received ) As-welded
P_APP_T01 P_APP_T00
100 250 120 50
As-received 60 120 100 750 120
As-welded 50 300
P_APP_T02 P_APP_T01
100 250
100 Protected120
250 until reach50
room temperature
60 120 100100 750
750 120 120 50 50 300 300
P_APP_T03 100 250 120 50 60 120 100 750 120 50 300
P_APP_T08 P_APP_T02
100 250 120 50 Protected until
20 reach room– 100100 750
100 250 750 120 120 50 50 300 300
temperature
P_APP_T03 100 250 120 50 60 120 100 750 120 50 300
The purpose
P_APP_T08of this100 test is
250 to verify
120 to what
50 extent
20 hydrogen,
-- 100 if 750
inserted 120 into50the weld,
300 interferes
with the joint together with the internal stress and corrosion in the weld. It is well known that the lack
The purpose of this test is to verify to what extent hydrogen, if inserted into the weld, interferes
of tempering withofthethis
jointmaterial afterthewelding
together with for extended
internal stress periods
and corrosion in the can
weld.be It detrimental.
is well known that This
theis because,
due to their lack of tempering of this material after welding for extended periods can be detrimental. This is stresses
late performance, the welds have a microstructure that is susceptible to internal
because, due
and often external to theirwhich,
stresses late performance,
togetherthe welds
with have a microstructure
a certain that is susceptible
level of hydrogen, can result to internal
in cold cracking,
stresses and often external stresses which, together with a certain level of hydrogen, can result in cold
which is also known as hydrogen cracking. Apart from the presence of these agents, it is possible that
cracking, which is also known as hydrogen cracking. Apart from the presence of these agents, it is
welds maypossible
also bethat
subject to corrosion,
welds may which
also be subject may lead
to corrosion, to may
which stress
leadcracking in addition
to stress cracking to cold
in addition to cracking.
This was the coldmain reason
cracking. This to
wasinclude
the maina reason
waiting periodaof
to include 6 months
waiting periodafter the welding
of 6 months after theand before PWHT.
welding
Figure and2 before
shows PWHT.
the setup used to perform the preheating process (a), as well as the welding
Figure 2 shows the setup used to perform the preheating process (a), as well as the welding
process (b).
Metals 2020, 10, x FOR PEER REVIEW 9 of 24
process (b).

(a) (b)

Figure 2. (a) Pipes preheating setup and (b) Pipe welding.

The characterization of the joints has been carried out following different techniques with a view
to get important information about the properties achieved by the samples under each set of thermal
cycles used. Thus, the characterization techniques used can be seen below, as well as the main reasons
behind their selection.
• Liquid penetrant testing: used after the chamfer preparation;
Metals 2020, 10, 99 9 of 23

The characterization of the joints has been carried out following different techniques with a view
to get important information about the properties achieved by the samples under each set of thermal
cycles used. Thus, the characterization techniques used can be seen below, as well as the main reasons
behind their selection.

• Liquid penetrant testing: used after the chamfer preparation;

• Visual testing: immediately before the welding process, checking the morphology of the welds
and possible external defects;
• X-ray analysis: looking for internal defects;
• Hardness surface testing: checking for possible deviations regarding the expected values;
• Bending tests: trying to explore the appearance of eventual defects when loaded by bending;
• Tensile testing at 20 ◦ C: checking the mechanical strength of the joint at room temperature;
• Tensile testing at 600 ◦ C: checking the mechanical strength of the joint at high temperature;
• Hardness profile: analyzing the hardness along the cross-section of the welds;
• Chemical composition: trying to characterize the weld’s composition;
• Electronic and optical microscopy: observing the resulting microstructure;
• Microhardness: trying to identify soft spots, where Type IV cracking usually appears.

After welding, the samples were immediately subjected to a first check in order to verify if the samples
met the acceptance criteria defined in EN ISO 5817–Level C [33]. Afterwards, an additional visual
inspection following ISO-17637:2003 standard [34] was performed, getting the corresponding approval.
After that, samples were checked using liquid penetrant following the ISO 3452-1:2013 [35], looking for
defects that had reached the surface. Since all the samples did not present surface signs of defects,
they obtained the corresponding approval. Trying to detect internal defects, the samples also were
subjected to X-ray inspection following the ISO 20769-2:2018 standard [36], using an ICM machine with
300 kVA, obtaining the corresponding approval as well. Indeed, some samples presented an excess
of penetration, which is a defect that is acceptable, but there were no other defects such as root lack
of penetration, porosities, or inclusions. The criteria used to approve the welds also followed ASME
Code Sections I, V, VIII Div. 1 and 2, ASME B31.1 [37]. After these previous non-destructive tests, the
samples were cut and machined in a vertical milling machine Baileigh VM-1054-3. A summary of these
previous tests can be seen in Figure 3. After machining, it was necessary to smooth the weld until it is
leveled with the base material, so that the entire test area was of the same thickness and section in
order to remove the notch factor resulting from the border of the bead with the base material. This
operation was performed for the tensile and bend samples.
In order to perform the other tests, different equipment was used, which is described as follows.
Regarding the hardness assessment, three different tests were performed: hardness tests with portable
equipment to carry out a first evaluation of the welded joints, a microhardness cross-section evaluation
in order to assess the hardness reached in each zone of the joint, and finally another microhardness test
allowing the detection of soft spots. Thus, the surface preparation was carried out using sandpaper
provided with different grain sizes (80, 220, 310, 500, and 1000 mesh) until the Rz roughness parameter
was lower than 5 µm. A Krautkramer–MIC 10 equipment provided with a MIC 205-A probe was
used because it is portable and easy to handle, providing results accurate enough regarding the level
required at this stage, which was just a general previous evaluation. The load used to perform these
tests was 49 N (5 kgf) with a dwell time of 30 s, and a diamond Vickers indenter with 136◦ was used to
perform the indentations. In order to obtain more accurate results, further microhardness tests were
carried out using Shimadzu HSV-20 equipment, following the NP EN 1043-1 standard, using as the
load 98.1 N (10 kgf) and a Vickers diamond indenter. However, to do that, it was necessary to improve
the surface roughness through a new polishing process with diamond slurry of 1 µm over 10 min in
order to decrease the Rz roughness to values under 2 µm. Two rows of indentations were produced as
depicted in Figure 4. Finally, the opposite surface of the same samples was prepared following the
same procedure as well, in order to identify soft spots close to the base material. Indeed, Newell [38]
Metals 2020, 10, 99 10 of 23

argues that these soft points are responsible for a decrease in creep resistance by about 20% compared
to an unaffected base material and are formed mainly in the fine grain region of the HAZ. Using the
same microhardness equipment and indenter, these tests have been carried out using just 1 kgf (HV1 )
and a dwell time of 30 s, still following the ISO 6507:2018 standard [39]. Three rows of indentations
were produced, one close to the weld root, another in the middle of the cross-section, and the last
one close to the surface of the base material; all of the indentations were distanced 0.5 mm each other,
which is the minimum distance recommended by the standard, avoiding the influence on the results
among indentations. This value was selected based on a good compromise between the lowest value
recommended for this effect and the small grain size usually observed close to the HAZ. In this case,
just oneMetals
sample was analyzed regarding each set of welding and heat-treatment conditions.
2020, 10, x FOR PEER REVIEW 10 of 24

(a) (b)

Metals 2020, 10, x FOR PEER REVIEW 11 of 24

middle of the cross-section, and the last one close to the surface of the base material; all of the
indentations were distanced 0.5 mm each other, which is the minimum distance recommended by
(c) (d)
the standard, avoiding the influence on the results among indentations. This value was selected based
on a Figure Figure 3. Differentbetween
good compromise
3. Different non-destructive
the test
non-destructive stages
lowest regarding
test value the samples approval:
stagesrecommended
regarding the for (a) Liquid
this
samples penetrant
effect andbefore
approval: the
(a) small
Liquidgrain
welding; (b) Dimensional control; (c) Liquid penetrant after welding and cutting; (d) X-ray analysis.
size usually
penetrantobserved close to(b)
before welding; theDimensional
HAZ. In this case, just
control; one sample
(c) Liquid wasafter
penetrant analyzed
weldingregarding each set
and cutting;
of welding and
(d) X-ray heat-treatment
analysis. conditions.
In order to perform the other tests, different equipment was used, which is described as follows.
Regarding the hardness assessment, three different tests were performed: hardness tests with
portable equipment to carry out a first evaluation of the welded joints, a microhardness cross-section
evaluation in order to assess the hardness reached in each zone of the joint, and finally another
microhardness test allowing the detection of soft spots. Thus, the surface preparation was carried out
using sandpaper provided with different grain sizes (80, 220, 310, 500, and 1000 mesh) until the Rz
roughness parameter was lower than 5 μm. A Krautkramer–MIC 10 equipment provided with a MIC
205-A probe was used because it is portable and easy to handle, providing results accurate enough
regarding the level required at this stage, which was just a general previous evaluation. The load
used to perform these tests was 49 N (5 kgf) with a dwell time of 30 s, and a diamond Vickers indenter
with 136° was used to perform the indentations. In order to obtain more accurate results, further
microhardness tests were carried out using Shimadzu HSV-20 equipment, following the NP EN 1043-
1 standard, using as the load 98.1 N (10 kgf) and a Vickers diamond indenter. However, to do that, it
was necessary to improve the surface roughness through a new polishing process with diamond
slurry of 1 μm over 10 min in order to decrease the Rz roughness to values under 2 μm. Two rows of
indentations
Figure were produced as depicted in Figure 4. Finally, the opposite surface of the same samples
Figure 4.
4. Example
Example on on how
how the
the microhardness
microhardness indentations
indentations were produced
were produced across
across the
the cross-section.
cross-section.
was prepared following the same procedure as well, in order to identify soft spots close to the base
In material.
order toIndeed,
analyzeNewell [38] argues that these soft points are responsible for a decrease in creep
the chemical composition of the weld, an optical emission spectrometer
resistance by about 20% compared to an unaffected base material and are formed mainly in the fine
Spectro,grain
model Spectrolab M8 was used. This test was performed trying to understand the
region of the HAZ. Using the same microhardness equipment and indenter, these tests have
composition of the weld and
been carried out using just corresponding
1 kgf (HV1) anddilution. Theofvalues
a dwell time achieved
30 s, still arethe
following based on six analyses
ISO 6507:2018
in different samples,
standard androws
[39]. Three the of
results presented
indentations are average
were produced, one values
close to with standard
the weld deviations
root, another in the lower
Metals 2020, 10, 99 11 of 23

In order to analyze the chemical composition of the weld, an optical emission spectrometer Spectro,
model Spectrolab M8 was used. This test was performed trying to understand the composition of the
weld and corresponding dilution. The values achieved are based on six analyses in different samples,
and the results presented are average values with standard deviations lower than 5%.
The micrographic analysis aims to analyze the microstructure present in the samples, thus allowing
verification of the grain size and its distribution. In order to perform these analyses, a Carl Zeiss
(Carl Zeiss, Oberkochen, Germany) optical microscope model Axioskop 2 Mat was utilized, using
different lens and magnifications. This analysis was also an important tool to verify the influence
of thermal cycles on the steel microstructure, both in melted zone (MZ) and the HAZ. This optical
microscopy technique is ideal for microstructure analysis, grain size analysis, particle analysis, and the
identification of voids or cracks. For this purpose, the samples were prepared by sanding and polishing
with 80 mesh sandpapers, followed by 220, 310, 500, and finally 1000 mesh. Then, the samples were
polished sequentially with 3 µm and 1 µm diamond slurry, after which the samples were etched
using a reagent called Vilella, which consists of hydrochloric acid, 5 mL; picric acid, 2 g; and ethyl
or methyl alcohol, 100 mL. The etching time was 20 s. The test was performed according to BS EN
1321:1997—Destructive test on welds in metallic materials—Macroscopic and microscopic examination
of welds [40].
Tensile tests allow a vast characterization of the materials, both in terms of mechanical strength
and ductility. Moreover, this type of test can be performed at different temperatures, simulating hard
work conditions that can be applied to the materials and joints in service. In this case, tensile tests were
performed at room temperature, 20 ◦ C, and at high temperature, 600 ◦ C, from which yield strength,
rupture and elongation data were collected. In order to increase the confidence in the values collected,
three tests were carried out for each condition considered in this work. In order to perform the tensile
tests, as Instron universal testing machine model 4208 was used, which was provided with a load cell
of 300 kN. Tensile test specimens were taken from the weld cross-section and prepared according to
ASME IX: 2015–QW 150 [41]. Regarding the tensile tests carried out at elevated temperature (600 ◦ C),
they were performed in a similar universal testing machine (Instron 8562) provided with a heated
camera where the samples are kept at constant temperature during the tensile tests. The load cell used
is a 100 kN cell. The samples were prepared following the ISO 6892-2:2018 standard [42].
Bending tests are usual in welded samples because they allow the assessment of the samples’
behavior under very demanding work circumstances. In this work, bending tests were performed
using a hydraulic CIATA press, model P-115/HP provided with a maximum compression capacity of
147 kN (15 tons). Samples were tested according to ASME IX–QW163 [43], with a bending angle of
180◦ , a bearing distance of 36 mm, and a spindle diameter of 24 mm. Samples were used in which the
compressive effort was performed on the welding face and others were performed on the welding root
to cover all situations. After the tests, the samples were analyzed using the penetrant liquid technique,
which was previously described in this work.

3. Results and Discussion

3.1. Non-Destructive Test Results

Some of the initially performed tests were merely qualitative, thus providing information about
whether the samples were ready to pursue the analysis or not. These tests were already described
before in this work.

3.2. Hardness and Microhardness Analyses

The hardness tests performed allowed assessing the hardness profile across the joint, from the
base material 1 (BM1) to the base material 2 (BM2), passing by the thermal-affected zones 1 and 2
(HAZ1 and HAZ2) and the melted zone (MZ). The microhardness values can be observed in Table 6,
and the profiles corresponding to the different samples can be seen in Figure 5, resulting from the
Metals 2020, 10, 99 12 of 23

average values of five samples measured in the same places (15 indentations per sample), taking into
account the central area of each sample. The calculated standard deviation can be observed in Table 6
as well. The letter B included in the label of samples P_APP_T02 and P_APP_T03 in Figure 5 represents
the values obtained before the PWHT was carried out six months after the welding and corresponding
heat treatments performed in the first stage of the samples’ preparation. As expected, the hardness
values before PWHT are higher in the HAZ and MZ, because the martensite is not tempered yet, being
extremely hard in that state. After PWHT, the values achieved are within the expected range. Since
the sample P_APP_T00 was not subjected to heat treatments, its hardness is extremely high in the
MZ, as well as in the HAZ. Thus, sample P_APP_T00 does not fulfill the properties required by the
usual applications of this kind of material, and the procedure used in this sample can be considered
inadequate. It is worth noticing that the remaining samples show hardness values within the usual
range for this material; thus, at this stage, excluding the P_APP_T00 sample, the other samples can
be considered for the next tests. Performing this test only lets us validate in a first moment, in the
shop floor, the ability of the work pieces to advance to the next stages, because the accurateness of
the hardness measuring equipment is ±40 HV. Thus, in order to evaluate the surface hardness of
the samples with adequate accuracy, microhardness tests were performed using the microhardness
measuring equipment previously described. The microhardness profile can be seen in Figure 6,
showing clearly that sample P-APP_T00 presents a different hardness behavior resulting from the lack
of heat treatments. In this case, the microhardness measurements were performed only after the PWHT
treatment; thus, there are no curves corresponding to this situation, as shown in Figure 5. The values
reported in the curves can be considered common for this kind of material and joint. The increased
hardness reported in the MZ and HAZ is typical (250–280 HV10 ) as well in these conditions, and the
values registered are within the range of acceptable values (200–275 HV10 , but they can reach 300 HV10
without special concerns). Excluding the sample P_APP_T00, which presents a singular behavior due
to the absence of heat treatments before the PWHT applied to this sample, the samples were mainly
constituted of non-tempered martensite, which was hard and brittle. The pattern followed by the
remaining samples is very similar among them, with microhardness values of around 230 HV10 in the
base metal and slighting increasing across the HAZ, reaching steady values between 250 and 280 HV10
in the MZ. Obviously, sample P_APP_T00 is not acceptable, reaching microhardness values out of the
range of acceptable values. This corroborates the unconditional need for applying heat treatments to
this base material when welding is included in the manufacturing processes. According to ISO 18265
(Metallic materials—Conversion of hardness values), it is possible to estimate the ultimate strength
through hardness values [34]. This is because both hardness and ultimate strength are indicators of
the mechanical resistance of a metal to plastic deformation, and they are approximately proportional.
However, this proportionality is not valid for all metals. For this case, it may be pointed out that the
breaking stress in MPa is 3.13 times higher than the hardness in HV.

Table 6. Surface microhardness of the different samples (HV10 ). HAZ: heat-affected zone, MZ:
melted zone.

BM1 HAZ1 MZ HAZ2 BM2

Samples Ref.
HV10
P_APP_T00 207 ± 5 271 ± 12 356 ± 16 292 ± 8 211 ± 12
P_APP_T01 199 ± 17 198 ± 20 245 ± 12 208 ± 16 196 ± 14
P_APP_T02 212 ± 11 268 ± 14 327 ± 9 278 ± 13 214 ± 9
P_APP_T03 204 ± 8 287 ± 12 310 ± 11 288 ± 8 206 ± 10
P_APP_T08 195 ± 6 195 ± 7 212 ± 9 191 ± 5 193 ± 3
 BM1 HAZ1 MZ HAZ2 BM2
Samples Ref.
HV10
P_APP_T00 207 ± 5 271 ± 12 356 ± 16 292 ± 8 211 ± 12
P_APP_T01 199 ± 17 198 ± 20 245 ± 12 208 ± 16 196 ± 14
P_APP_T02 212 ± 11 268 ± 14 327 ± 9 278 ± 13 214 ± 9
Metals 2020, 10, 99 P_APP_T03 204 ± 8 287 ± 12 310 ± 11 288 ± 8 206 ± 10 13 of 23
P_APP_T08 195 ± 6 195 ± 7 212 ± 9 191 ± 5 193 ± 3

Figure 5. Hardness profile of the different samples across the welded and neighboring areas. The label
Figure 5. Hardness profile of the different samples across the welded and neighboring areas. The label
B in some graphs represents the values obtained before the PWHT was carried out 6 months after the
B in some graphs represents the values obtained before the PWHT was carried out 6 months after
welding.
theMetals
welding.
2020, 10, x FOR PEER REVIEW 14 of 24

Figure 6. Microhardness profile of the different samples across the welded and neighboring areas.
Figure 6. Microhardness profile of the different samples across the welded and neighboring areas.
The microhardness tests were also performed having as the main goal identifying soft spots in
The microhardness tests were also performed having as the main goal identifying soft spots in the
the cross-section, i.e., very small areas where the hardness is lower than in the base metal or in the
cross-section, i.e., very small areas where the hardness is lower than in the base metal or in the fine
fine grain region of the HAZ, which is also known as the intercritical region. The summary of the
grain region
results bythe
of theHAZ,
crossedwhich
regionis also
can known
be seen as the
in Table intercritical
7. The intercriticalregion.
region isThe summary
located of the results by
in the connection
the crossed
zone region can be
of the HAZ, seen
which in Table
is very close7.
to The intercritical
the base region
material. This is located
is where in theType
the so-called connection
IV crack zone of
usually appears, which often occurs both at the manufacturing stage and
the HAZ, which is very close to the base material. This is where the so-called Type IV crack during the life of the usually
component.
appears, which often occurs both at the manufacturing stage and during the life of the component.
Table 7. Cross-section microhardness of the different samples (HV1).
Table 7. Cross-section microhardness of the different samples (HV1 ).
BM (Left) HAZ (Left) MZ HAZ (Right) BM (Right)
Samples Ref.
BM (Left) HAZ (Left) MZ HAZ (Right) BM (Right)
Samples Ref. HV10
P_APP_T00 231 ± 2 422 ± 45 404 ±HV
12 10 439 ± 23 231 ± 4
P_APP_T01 219 ± 6 242 ± 19 253 ± 6 230 ± 15 218 ± 2
P_APP_T00 231 ± 2 422 ± 45 404 ± 12 439 ± 23 231 ± 4
P_APP_T02 222 ± 2 242 ± 19 272 ± 6 247 ± 17 223 ± 2
P_APP_T01 219 ± 6 242 ± 19 253 ± 6 230 ± 15 218 ± 2
P_APP_T03 224 ± 2 243 ± 21 266 ± 5 242 ± 18 225 ± 2
P_APP_T02 222 ± 2 242 ± 19 272 ± 6 247 ± 17 223 ± 2
P_APP_T08 227 ± 3 231 ± 13 271 ± 6 247 ± 18 234 ± 2
P_APP_T03 224 ± 2 243 ± 21 266 ± 5 242 ± 18 225 ± 2
P_APP_T08 227
Regarding the soft ± 3analysis,231
spot no ± 271 ±was
13 attention
special the±P_APP_T00
6 paid to247 18 234 ± 2due
samples,
to its non-heat-treated condition. Taking into attention the P_APP_T01 samples, lower microhardness
values were identified in the range of 7.5 to 10 mm from the center line of the weld. Indeed, this is
the most critical area in the weld cross-section because this is a HAZ that is close to the base material,
which is an area that is well known as the region where the grain size is finer and the hardness can
drop about 20 HV of the substrate’s usual level. Regarding the samples P_APP_T01, some
microhardness measurements provided values under 200 HV (187 HV, while the base material
Metals 2020, 10, 99 14 of 23

Regarding the soft spot analysis, no special attention was paid to the P_APP_T00 samples, due to
its non-heat-treated condition. Taking into attention the P_APP_T01 samples, lower microhardness
values were identified in the range of 7.5 to 10 mm from the center line of the weld. Indeed, this is
the most critical area in the weld cross-section because this is a HAZ that is close to the base material,
which is an area that is well known as the region where the grain size is finer and the hardness can drop
about 20 HV of the substrate’s usual level. Regarding the samples P_APP_T01, some microhardness
measurements provided values under 200 HV (187 HV, while the base material presents 220–230 HV)
in the intercritical area, indicating that there are soft spots that can induce Type IV cracks. The samples
P_APP_T02 and P_APP_T03 did not present values under 200 HV. Indeed, the lowest value obtained
in both samples was 204 HV, showing that these samples do not present soft spots and are not prone to
develop Type IV cracks in the intercritical area. The sample P_APP_T08 presented just one (one in
14) value below 200 HV (170 HV), which was located into the HAZ and close to the surface. Since all
the other results were close to 220 HV in this sample, the result was not valued also because in the
root and middle indentations rows, the same effect was not felt. Thus, it was considered that sample
P_APP_T08 presents good conditions to avoid the development of Type IV cracks, presenting less
concerns than sample P_APP_T01.

3.3. Welds Chemical Analysis

In order to check the final composition of the weld, optical spectroscopy was used to obtain the
weld composition. However, as the chemical composition of the base material and filler metal are very
similar, it would be expected that the weld follows a chemical composition very similar to the base
material and filler metal. The results can be seen in Table 8, where the compositions related to Pipe 1,
Pipe 2, and the filler metal have been taken from the information provided by the suppliers and the
composition related to the weld face and root face were taken from analyses performed by optical
spectroscopy. As can be observed, the chemical composition of the weld, both in the face and in the
root, are very similar to the compositions provided by the suppliers to the base materials and filler
metal. Thus, the dilution in the welding process will not significantly affect the weld composition.

Table 8. Chemical analysis of the materials used in the welding and the weld composition (wt %).

Material Reference C Si Mn P S Al Cr Ni Mo V
Pipe 1 SA 213 T91 0.091 0.35 0.52 0.016 0.0011 0.006 8.71 0.28 0.95 0.21
Pipe 2 SA 213 T91 0.102 0.29 0.50 0.017 0.0012 0.009 8.60 0.17 0.98 0.23
Filler metal ER 90S B9 0.092 0.22 0.54 0.008 0.0020 - 8.90 0.46 0.90 0.22
Weld face - 0.095 0.29 0.55 0.007 0.0006 0.005 8.88 0.48 0.89 0.22
Weld root - 0.091 0.30 0.53 0.010 0.0008 0.005 8.90 0.42 0.89 0.22

3.4. Microstructure Analysis

The microstructure analysis gives relevant information about the behavior of the different zones
of the welds’ cross-section. Thus, each sample was carefully analyzed, allowing a deep understanding
of the phenomena produced by the different thermal cycles applied to the samples. A vast number
of micrographs were collected, sorted, and analyzed, and the selection of the most representative
micrographs regarding each sample and area of analysis are presented in Figure 7.
All the micrographs present microstructures consisting of tempered martensite, which gives the
joint very good properties, excluding the P_APP_T00 sample. This presents a microstructure with
martensite, but it is not tempered, because the PWHT was not performed. Samples P_APP_T01,
P_APP_T02, and P_APP_T03 present very similar microstructures with identical grain sizes. Precipitates
are found along the grain boundaries. The typical grain size in the HAZ is about 20–30 µm, and in the
MZ it appears larger, with grains of 60–70 µm. In sample P_APP_T01, the grains appear more defined,
and the martensite areas appear tempered as well. The sample P_APP_T08 presents a regular HAZ;
however, the MZ presents an atypical structure relative to the other samples used in this work. This
 Filler metal ER 90S B9 0.092 0.22 0.54 0.008 0.0020 - 8.90 0.46 0.90 0.22
Weld face - 0.095 0.29 0.55 0.007 0.0006 0.005 8.88 0.48 0.89 0.22
Weld root - 0.091 0.30 0.53 0.010 0.0008 0.005 8.90 0.42 0.89 0.22

3.4. Microstructure Analysis

Metals 2020, 10, 99 15 of 23
The microstructure analysis gives relevant information about the behavior of the different zones
of the welds’ cross-section. Thus, each sample was carefully analyzed, allowing a deep understanding
of the
reveals thatphenomena produced can
the creep behavior by the different
limit thermal cycles
the application applied
of this kindtoofthe samples.
joint A vast
in classic number of
applications
of micrographs were collected, sorted, and analyzed, and the selection of the most representative
this kind of material, but this expectation needs to be confirmed.
micrographs regarding each sample and area of analysis are presented in Figure 7.
Sample

BM HAZ MZ
P_APP_T00
P_APP_T01

Metals 2020, 10, x FOR PEER REVIEW 16 of 24

P_APP_T02
P_APP_T03
P_APP_T08

Figure 7. Micrographs of the different cross-section areas for samples subjected to different thermal
Figure 7. Micrographs of the different cross-section areas for samples subjected to different thermal
cycles. Blue arrows highlight grain boundaries and green arrows highlight precipitates.
cycles. Blue arrows highlight grain boundaries and green arrows highlight precipitates.
All
3.5. Tensile the micrographs
Tests at Room and present microstructures consisting of tempered martensite, which gives the
High Temperature
joint very good properties, excluding the P_APP_T00 sample. This presents a microstructure with
The ASMEbut
martensite, IX: it2013–QW 150 [41]because
is not tempered, code refers to 585was
the PWHT MPanotasperformed.
the minimum yield
Samples strength to be
P_APP_T01,
P_APP_T02,
achieved in weldsand P_APP_T03
of this present very
kind of material; similar
this is microstructures
the value with identical
that is also required grain sizes.
as a minimum for the
Precipitates are found along the grain boundaries. The typical grain size in the HAZ is about
base material. Regarding yield strength and elongation, the code does not specify any minimum value. 20–30
ASME μm, andB31.3—Process
code in the MZ it appears
Pipinglarger, with grains
[37] refers of 60–70yield
to minimum μm. In sample
stress 413P_APP_T01, the grains
MPa and ultimate tensile
appear more defined, and the martensite areas appear tempered as well. The sample P_APP_T08
presents a regular HAZ; however, the MZ presents an atypical structure relative to the other samples
used in this work. This reveals that the creep behavior can limit the application of this kind of joint
in classic applications of this kind of material, but this expectation needs to be confirmed.

3.5. Tensile Tests at Room and High Temperature

Metals 2020, 10, 99 16 of 23

strength 586 MPa. Analyzing the rupture results, it was found that it always occurred in the base
material at a considerable distance from the welding area, as can be seen in Figure 8. Moreover, all
ruptures presented a ductile look, even when the elongation was relatively low. The values obtained in
the tensile tests can be observed in Table 9, namely the yield strength, ultimate tensile strength, and
elongation at room and high temperature. The results can be observed in Figures 9 and 10. The highest
values are presented by sample P_APP_T00, because they were not subjected to heat treatments and
PWHT. Thus, the yield strength and ultimate strength are the highest values, but the elongation
presents
Metals
Metalsthe
2020,
2020,lowest
10, x FOR
10, values,
PEER
x FOR although these were not significantly different from samples P_APP_T02,
REVIEW
PEER REVIEW 17 17 of 24
of 24
P_APP_T03, and P_APP_T08. Sample P_APP_T03 presents the lowest ultimate strength value at room
value at at
room
roomtemperature,
temperature,and
and P_APP_T02
P_APP_T02 presents the lowest
lowestultimate
ultimatestrength
value at strength value
value presents the value at at
highhigh
temperature, and P_APP_T02 presents the lowest ultimate strength high temperature.
temperature.
temperature.

Figure 8. Aspect of the samples used in tensile tests after rupture. Line 2 indicates the welding zone.
Figure 8. Aspect of the samples used in tensile tests after rupture. Line 2 indicates the welding zone.
Figure 8. Aspect of the samples used in tensile tests after rupture. Line 2 indicates the welding zone.
Table
Table 9. Yield
9. Yield strength,
strength, ultimatetensile
ultimate tensilestrength,
strength, and
andelongation
elongationatatroom
roomandandhigh temperature.
high temperature.
Table 9. Yield strength, ultimate tensile strength, and elongation at room and high temperature.
Room Temperature (20 °C) High Temperature (600 °C)◦
Room Temperature (20 ◦ C) High Temperature (600 C)
Samples Samples Room
Rp 0.2 Temperature
Rm (20 °C)
Elong. High
Rp0.2 Temperature
Rm (600 °C)
Elong.
Rp0.2 Rm Elong. Rp0.2 Rm Elong.
Samples RpMPa
0.2 MPa
Rm %
Elong. MPa
Rp0.2 MPa
Rm %
Elong.
P_APP_T00MPa 559
MPa ± 16 MPa 696
MPa± 15 14.5 %% ± 0.4 350 MPa ± 12 405
MPa MPa
± 9 14.4 ±%
MPa 0.3 %
P_APP_T01
P_APP_T00
P_APP_T00 526
559
559 ± ± 7
16± 16696696 696 ± 3 24.8
± 15 14.5
± 15 14.5 ± 0.9
± 0.4 350
± 0.4 331 ± 6 377
350±±1212 405 ± 8 16.3 ±
405 ±±99 14.414.40.8
± 0.3± 0.3
P_APP_T02
P_APP_T01526 ±
P_APP_T01 511
526 ± 2
7 ± 7 696696666 ± 1
± 3± 3 24.816.5 ±
± 0.9
24.8 1.2
± 0.9 331 235 ± 3
331±±66 377239 ± 3 15.8 ±
377 ±±88 16.316.30.9
± 0.8± 0.8
P_APP_T03
P_APP_T02
P_APP_T02 511 ±509
5112 ±±22 666666
548
± 1±± 11 16.5
17.6
± ±1.2
16.5 ± 0.3
1.2 235287
235±±±323 345 ± ±3±33 18.3
239
239 15.8±15.8
0.4
± 0.9± 0.9
P_APP_T03
P_APP_T08 509 ±515
2 ± 5 548682 ± 1 ± 8 17.6 ± ±0.30.9 287
15.1 301±± 25 362 ± 6± 3 16.7 ±18.3
345 0.8 ± 0.4
P_APP_T03 509 ± 2 548 ± 1 17.6 ± 0.3 287 ± 2 345 ± 3 18.3 ± 0.4
P_APP_T08 515 ± 5 682 ± 8 15.1 ± 0.9 301 ± 5 362 ± 6 16.7 ± 0.8
P_APP_T08 515 ± 5 682 ± 8 15.1 ± 0.9 301 ± 5 362 ± 6 16.7 ± 0.8

Figure 9. Results of the tensile tests performed at room temperature.

Figure 9. Results of the tensile tests performed at room temperature.

Figure 9. Results of the tensile tests performed at room temperature.
Metals 2020, 10, 99 17 of 23

Metals 2020, 10, x FOR PEER REVIEW 18 of 24

Figure 10. Results of the tensile tests performed at elevated temperature (600 °C).
Figure 10. Results of the tensile tests performed at elevated temperature (600 ◦ C).

Regarding
Regarding thethe results
results obtained
obtained at elevated
at elevated temperature,
temperature, ASMEASME B31.3—Process
B31.3—Process Piping
Piping codecode
refers
to the minimum yield strength of 71 MPa at a temperature of 600 C [37]. In some codes, this this
refers to the minimum yield strength of 71 MPa at a temperature of
◦ 600 °C [37]. In some codes, value
value may be higher, requiring a minimum of 215 MPa. In any case, the results presented are above
may be higher, requiring a minimum of 215 MPa. In any case, the results presented are above these
these minimum values for both codes cited. As in the tests carried out at room temperature, the
minimum values for both codes cited. As in the tests carried out at room temperature, the samples also
samples also presented a ductile rupture clearly out of the MZ or HAZ.
presented a ductile rupture clearly out of the MZ or HAZ.
Regarding Table 9, and excluding the sample P_APP_T00 which presents high risks of cracking
Regarding Table 9, and excluding the sample P_APP_T00 which presents high risks of cracking in
in service due to its structure in the HAZ, and considering the sample P_APP_T01 as the model
service duerecommended
usually to its structurebyinthe
the main
HAZ,steel
and manufacturers
considering theand sample P_APP_T01
construction codes,as the
the model
sampleusually
that
recommended
presents the closest yield and ultimate strength both at room and elevated temperaturespresents
by the main steel manufacturers and construction codes, the sample that is samplethe
closest yield and
P_APP_T08. Theultimate strengthpresented
main drawback both at room
by thisand elevated
sample is thetemperatures
low elongationiswhich,
sample P_APP_T08.
being higher
Thethan
main drawback presented by this sample is the low elongation which, being
that in the samples P_APP_T02 and P_APP_T03, is relatively lower than sample P_APP_T01. higher than that in the
samples
Indeed,P_APP_T02
P_APP_T01 and
is P_APP_T03,
the sample thatis relatively
presents alower than
better sample
relation P_APP_T01.
between mechanicalIndeed, P_APP_T01
strength and
is the samplemainly
ductility, that presents
at roomatemperature.
better relation betweenatmechanical
However, strength andthe
elevated temperature, ductility,
elongation mainly at room
decreases
temperature.
substantially However, at elevated
and reaches temperature,
similar values the elongation
to the other decreases
samples. Sample substantially
P_APP_T03 is theand
onereaches
that
similar values
presents theto theelongation
best other samples. Sample
at elevated P_APP_T03but
temperature, is the one that presents
its mechanical the best
resistance elongation
decreases more at
than that
elevated of the P_APP_T01
temperature, and P_APP_T08
but its mechanical samples.
resistance decreasesAt this
morestage, samples
than that of the P_APP_T02
P_APP_T01 andand
P_APP_T03
P_APP_T08 can be discarded,
samples. because
At this stage, they present
samples P_APP_T02 a considerable drop in the
and P_APP_T03 canmechanical
be discarded, resistance
because
theyrelative
presentto the P_APP_T01 drop
a considerable sample.
in the mechanical resistance relative to the P_APP_T01 sample.

3.6.3.6. Bending
Bending Tests
Tests
After
After thethe bending
bending testshave
tests havebeen
beencompleted,
completed, thethe samples
samples were
wereinitially
initiallyobserved
observedwith with the naked
the naked
eye and subsequently subjected to penetrant liquid tests (Figure 11) to identify
eye and subsequently subjected to penetrant liquid tests (Figure 11) to identify the possible existence the possible existence
of of microcracks.In
microcracks. In fact,
fact, no
nocracks
cracksorormicrocracks
microcracks were found
were in any
found inofanytheofsamples in eitherinMZ,
the samples HAZ,
either MZ,
or BM. Penetrant testing is not usual in industrial terms to verify this kind of
HAZ, or BM. Penetrant testing is not usual in industrial terms to verify this kind of joint, as cracks joint, as cracks usually
develop quite rapidly and are perfectly noticable to the naked eye. However, the penetrant liquid
usually develop quite rapidly and are perfectly noticable to the naked eye. However, the penetrant
technique was used to confirm the absence of any kind of cracking in this work. All specimens
liquid technique was used to confirm the absence of any kind of cracking in this work. All specimens
described a perfect curvature, except for the sample P_APP_T00. These samples showed an atypical
described a perfect curvature, except for the sample P_APP_T00. These samples showed an atypical
curvature, where it can be seen that the MZ offered such high bending resistance that the curvature
curvature, where it can be seen that the MZ offered such high bending resistance that the curvature
took place in the BM. This effect is clearly depicted in Figure 12. Anyway, this sample does not present
took place in the BM. This effect is clearly depicted in Figure 12. Anyway, this sample does not present
any crack or discontinuity. Given that the P_APP_T00 sample presented high mechanical strength
anyand
crack
lowor discontinuity.
elongation, and thatGiven that the P_APP_T00
its microstructure consisted sample presented
essentially high mechanical
of non-tempered strength
martensite, it
andwould be expected that this samples would exhibit cracks when subjected to more intense it
low elongation, and that its microstructure consisted essentially of non-tempered martensite,
would be expected
deformation that this
stresses. samples
However, would
this exhibit
was not the cracks whenassubjected
case. Thus, a summary to more intense
of these tests,deformation
it can be
stresses. However, this was not the case. Thus, as a summary of these tests,
stated that all the samples are approved, but the P_APP_T00 sample shows greater resistance it can be stated that alltothe
samples
deformation in the weld bead zone, transfering the deformation to an adjacent zone (HAZ andthe
are approved, but the P_APP_T00 sample shows greater resistance to deformation in weld
BM).
bead zone, transfering the deformation to an adjacent zone (HAZ and BM).
(a) (b)
Metals 2020, 10, 99 18 of 23
Metals 2020,
Metals 2020, 10,
10, xx FOR
FOR PEER
PEER REVIEW
REVIEW 19 of
19 of 24
24

(a)
(a) (b)
(b)
Figure
Figure
Figure 11.Samples
11. Samples
11. Samples subjected
subjected
subjected to
toto bendingtests:
bending
bending tests:(a)
tests: (a)samples
(a) samplesbent
samples bent inin
bentin face
face and
and
face root
root
and surfaces,
surfaces,
root andand
and
surfaces, (b)liquid
(b) liquid
(b) liquid
penetrant
penetrant
penetrant technique
technique
technique applied
applied
applied to
to to
bentbent samples.
bentsamples.
samples.

(a)
(a) (b)
(b)
Figure
Figure
Figure 12. Bending
12. 12. Bending
Bending tests
tests
tests correspondingto
corresponding
corresponding to samples
to samples (a)
samples (a) P_APP_T08
(a)P_APP_T08
P_APP_T08and
and (b)(b)
(b)
and P_APP_T00.
P_APP_T00.
P_APP_T00.

3.7. Discussion
3.7. Discussion
3.7. Discussion about
about
about the
thethe Results
Results
Results andand
and Corresponding Thermal
Corresponding
Corresponding Thermal Cycles
Thermal Cycles
Cycles
After
AfterAfter collecting
collecting
collecting all the
all all
the the results
results
results andanalyzing
and
and analyzing them
analyzing them individually,
them individually,
individually,itit is itis now
now
is nownecessary
necessary
necessary to gather
to gather this this
this
to gather
information
information and relate it to the thermal cycles initially performed.
information andand relaterelate
it toit the
to the thermalcycles
thermal cyclesinitially
initially performed.
performed.
ItIt remains
remains clearclear that
that thethe welding
welding process
process generates
generates martensite
martensite in in the
the weld
weld andand HAZ,
HAZ, increasing
increasing
It remains clear that the welding process generates martensite in the weld and HAZ, increasing
the mechanical resistance, but limiting the ductility, as can be
the mechanical resistance, but limiting the ductility, as can be seen in the tensile tests and optical seen in the tensile tests and optical
the mechanical
microscopic resistance,
analysis but out
carried limiting
on the ductility,
sample P_APP_T00. asThis
canisbevalidseen for inboth
theroom
tensile tests andand
temperature optical
microscopic analysis carried out on sample P_APP_T00. This is valid for both room temperature and
microscopic
elevatedanalysis
elevated temperature,
temperature, carried which
which outcreates
on sample
creates P_APP_T00.
limitations
limitations regardingThis
regarding is
the use
the usevalid
of forkind
of this
this bothof
kind ofroom joint temperature
joint in their
in their
and elevated temperature,
traditional applications,
traditional applications, heat which creates
heat exchangers,
exchangers, due limitations
due to to creep regarding
creep phenomenon.
phenomenon. The the use of this
The microhardness kind
microhardness measured of joint
measured in their
traditional
clearlyapplications,
clearly confirms these
confirms theseheat
results,
results, exchangers,
showing an
showing andue to creep
increase
increase in phenomenon.
in hardness
hardness in the
in the MZMZThe andmicrohardness
and HAZ of
HAZ of these
these samples. measured
samples.
However,
clearly confirms
However, regarding
regarding thebending
these results,
the bending
showing tests,an
tests, noincrease
no cracks have
cracks have been
in been reported,
hardness
reported,in the butMZ
but thehigh
the high hardness
and hardness
HAZ presented
of these
presented samples.
in the
in
However, theregarding
weld moves
weld moves the
thethe bending
bending
bending center
center
tests, from the
from
no cracks the
have weld
weld been to the
to the base
base material.
reported, material.
but the high Thus,hardness
Thus, itit is
is clear
clearpresented
that
that
martensite
martensite needs
needs to
to be
be tempered
tempered after
after welding,
welding, and
and
in the weld moves the bending center from the weld to the base material. Thus, it is clear some
some heat
heat treatments
treatments can
can help
help to
to decrease
decrease the that
the
stress accumulated
stress accumulated in in and
and close
close toto the
the weld,
weld, improving
improving the the overall
overall mechanical
mechanical behaviorbehavior of of the
the joints.
joints.
martensite needs to be tempered after welding, and some heat treatments can help to decrease the
Sample P_APP_T01
Sample P_APP_T01 was was prepared
preparedfollowing
following the the codes’
codes’recommendations,
recommendations, including including preheating,
preheating,
stress accumulated in and close to the weld, improving the overall mechanical behavior of the joints.
post-heating, and
post-heating, and PWHT.
PWHT. The The procedure
procedure is is time
time consuming
consuming and and costly,
costly, but but the
the results
results are are excellent.
excellent.
Sample
The mechanical
The
P_APP_T01
mechanical was remains
resistance
resistance
prepared
remains within following
within the range
the
the codes’
range of values
of
recommendations,
values taken as
taken as acceptable
acceptable including
for this
for this kindpreheating,
kind of
of
post-heating,
joint, and
joint, and
and the PWHT.
the ductility
ductility is The procedure
is not
not severely is time
severely compromised, consuming
compromised, remaining and
remaining as costly,
as well but
well in the
in an results
an acceptable are
acceptable value, excellent.
value,
The mechanical
although itit is
although resistance
is more affected
more remains
affected withintemperatures
at elevated
at elevated the range ofthan
temperatures values
than takentemperature.
at room
at room as acceptable
temperature. The
Thefor this kind of joint,
microstructure
microstructure
and the
showsductility
shows the is notof
the presence
presence severely
of tempered
tempered compromised,
martensite, and
martensite, and remaining
the hardness
the hardness as values
well
valuesinareareanloweracceptable
lower than in
than invalue, casealthough
the case
the of the
of the it
P_APP_T00
P_APP_T00
is more samples.
affected samples.at elevated As expected,
As expected,
temperatures no cracks
no cracks
than have
have been developed
been
at room developed
temperature. during
during The or microstructure
or after the
after the bending
bendingshows tests. the
tests.
presence of tempered martensite, and the hardness values are lower than in the case of the P_APP_T00
samples. As expected, no cracks have been developed during or after the bending tests. Thus, the main
disadvantage of this procedure is the time spent to perform it and the energy consumed, making this
process less friendly to the environment.
Metals 2020, 10, 99 19 of 23

Sample P_APP_T02 was prepared saving the post-heating treatment and keeping the pre-heating
and PWHT. The phases’ transformation time included in the P_APP_T01 sample was suppressed
in this and the following thermal cycles. This thermal cycle gave interesting mechanical resistance
values at room temperature, but it did harm the ductility a little. However, analyzing the mechanical
resistance at elevated temperature, a severe decrease in the yield strength and ultimate strength can be
observed, presenting as well the lowest elongation value. Thus, suppressing the post-heat-treatment,
the properties at elevated temperature are severely affected. The grain seems to not be significantly
affected by the thermal cycles in the HAZ, and regarding the MZ, it seems to be less affected than
the other samples. Therefore, the absence of post-heat-treatment affects the properties at elevated
temperature, which is drastic for this kind of material regarding the typical applications referred above.
It is worth noting that no cold cracking effect was felt in the samples due to the waiting time imposed
between the welding process and PWHT.
The P_APP_T03 sample followed the same principles of the P_APP_T02 sample, but in this case,
a post-heat-treatment was included after the welding process and before the six-month waiting time.
These samples presented the lowest ultimate strength values at room temperature, although the values
relative to tensile at elevated temperature were improved relative to the similar P_APP_T02 sample.
This is the main concern of these samples. It is also worth noting that these samples present a very
good ductility behavior at room temperature and the best ductility at elevated temperature. At this
point, it needs to be referred that the only difference between the procedure applied to these samples
and the procedure used for sample P_APP_T01 is the inclusion of the six-month waiting time after the
post-heat-treatment and before the PWHT. However, the inclusion of this waiting time was detrimental
to the mechanical properties at room temperature, although other properties were improved, such as
the ductility.
Regarding the P_APP_T08 sample, the thermal cycles used are very similar to the thermal cycles
applied to P_APP_T01, having as the only difference suppression of the phases’ transformation time.
This suppression is important in terms of productivity and energy saving. The results obtained based
on these samples allow concluding that there is a good balance between the mechanical resistance
obtained and the ductility presented by these samples; both for room temperature and elevated
temperature, the grain is a little more acicular than in the other samples, which is not translated in
terms of hardness, which presents values extremely close to the average results obtained for samples
P_APP_T01, P_APP_T02, and P_APP_T03. Moreover, regarding the bending tests, no cracking or
its initiation has been detected. Thus, although these samples show a slight decrease in mechanical
resistance and ductility, this is a good alternative to the thermal cycle P_APP_T01.
In summary, Table 10 gives a brief overview of the thermal cycles applied to each set of samples
and the corresponding qualitative results, following the criteria pointed out at the bottom of Table 11.
It is worth noting that samples P_APP_T08 and P_APP_T01 present slight differences in the procedure,
as well as in the final results, not compromising the behavior of welds produced in this material in its
main applications.
Regarding the main parameters provided by tensile tests, and in order to make a decision regarding
the selection of the best strategy based on quantitative data, Table 11 was elaborated classifying from 1
to 4 (1 = worst value and 4 = best value) the different quantitative data obtained from that test. As
can be seen in Table 11, after the recommended procedure corresponding to the P_APP_T01 sample,
the best alternative is the P_APP_T08 strategy, with a sum of 6.1 points. This confirms the analysis
previously performed.
Metals 2020, 10, 99 20 of 23

Table 10. Summary of the thermal cycles applied and corresponding results by test type.

Thermal Cycles Performed Tests

Samples
Time Tensile Tensile
Preheating Post-Heating PWHT Hardness Macro Micro Bend
Transf. RT HT
Not Not
T00 No No No No Acceptable Good Good Good
Acceptable Acceptable
Very
T01 Yes Yes Yes Yes Very Good Very Good Very Good Very Good Good
Good
Not Very
T02 Yes No (1) No Yes (2) Good Very Good Good Acceptable
Acceptable Good
Not Very
T03 Yes Yes No Yes (2) Good Very Good Good Good
Acceptable Good
Very
T08 Yes Yes No Yes Good Acceptable Acceptable Good Good
Good
(1) Protected cooling until reaching room temperature; (2) PWHT performed 6 months after welding; Rating Scale:
Not Acceptable–Acceptable–Good–Very Good.

Table 11. Summary of the thermal cycles applied and corresponding results by test type.

Room Temperature (20 ◦ C) High Temperature (600 ◦ C)

Pts Total
Samples Rp0.2 Rp0.2 (Room +
Rm (MPa) A (%) Pts Rm (MPa) A (%) Pts
(MPa) (MPa) High)
Total Total
Value Pts Value Pts Value Pts Value Pts Value Pts Value Pts
P_APP_T01 526 4 696 4 24.8 4 4.00 331 3 377 4 16.3 3 3.60 7.60
P_APP_T02 511 2 666 2 16.5 2 2.00 235 1 339 1 15.8 2 1.15 3.15
P_APP_T03 509 1 548 1 17.6 3 1.30 287 2 345 2 14.6 1 1.85 3.15
P_APP_T08 515 3 682 3 15.1 1 2.70 301 4 362 3 16.7 4 3.40 6.10

4. Conclusions
Grade 91 steel is usually applied in situations where the temperature and pressure are very
demanding. The weldability of these steels presents well-known challenges, which are usually
overcome using complex thermal cycles before and after the welding process. This work intended
to test other thermal cycles with a view to shorten the treatment time, making the process more
productive and more environmentally friendly. Thus, five different thermal cycles were drawn and
tested: (a) welding without any pretreatment, post-treatment, or PWHT; (b) using the thermal cycle
recommended by the construction codes and steel manufacturers; (c) using a pretreatment and the
PWHT, using as well a six-month waiting period between welding and PWHT without phases’
transformation time, in order to study the possible development of cold cracking; (d) using the previous
strategy but including the post-welding treatment and; finally, (e) using the same strategy as that in (b)
but excluding the phases’ transformation time.
The hardness and microstructure assessed in P_APP_T00 indicate that this strategy cannot be
used, because if the mechanical strength is even higher than that in the P_APP_T01 case, the risks of
further cracking are higher, making this option not safe. The non-tempered martensite in the MZ and
HAZ induces a clear hardness increase, which can be capable of inducing further cracks in service.
Thus, this option was discarded due to these facts.
The last strategy (P_APP_T08) for thermal cycles around the welding process produced closer
results in terms of mechanical properties at both room and elevated temperatures, comparing with
the reference: P_APP_T01. A slight reduction in yield strength (2% at room temperature and 3.9% at
elevated temperature) and ultimate strength is reported (2% at room temperature and 9% at elevated
temperature), as well as a reduction of about 39% in the elongation at room temperature. However, at
elevated temperature, the elongation is even a little bit higher than in P_APP_T01 conditions. Since
this steel is usually used in high-temperature applications, this strategy seems to be the best among the
other strategies tested in this work.
Thus, the main contribution brought by this work can be stated as the development of a new
heat-treatment strategy to be applied in welding of grade 91 steels that is less time consuming and more
Metals 2020, 10, 99 21 of 23

environmentally friendly, providing very close results compared to the solution currently recommended
by construction codes and steel manufacturers.

Author Contributions: Conceptualization, A.P.P. and F.J.G.S.; methodology, A.P.P. and F.J.G.S.; validation, F.J.G.S.,
O.C.P. and A.B.P.; formal analysis, A.P.P.; investigation, A.P.P.; resources, A.P.P.; data curation, A.P.P. and F.J.G.S.;
writing—original draft preparation, F.J.G.S.; writing—review and editing, A.P.P., O.C.P. and A.B.P.; supervision,
F.J.G.S., O.C.P. and A.B.P. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors would like to thanks to ARSOPI company, which provided the best conditions
to carry out this work.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Pandey, C.; Mahapatra, M.M.; Kumar, P.; Saini, N. Some studies on P91steel and their weldments. J. Alloys
Compd. 2018, 743, 332–364. [CrossRef]
2. Standard, B. Seamless Steel Tubes for Pressure Purposes. Technical Delivery Conditions. Non-Alloy and Alloy Steel
Tubes with Specified Elevated Temperature Properties; BS EN 10216-2:2013; British Standards Institution: London,
UK, 2013.
3. Marzocca, A.L.; Luppo, M.I.; Zalazar, M. Identification of Precipitates in Weldments Performed in an ASTM
A335 Gr P91 Steel by the FCAW Process. Procedia Mater. Sci. 2015, 8, 894–903. [CrossRef]
4. Vidyarthy, R.S.; Dwivedi, D.K. Microstructural and mechanical properties assessment of the P91A-TIG weld
joints. J. Manuf. Process. 2018, 31, 523–535. [CrossRef]
5. Dhandha, K.H.; Badheka, V.J. Effect of activating fluxes on weld bead morphology of P91 steel bead-on-plate
welds by flux assisted tungsten inert gas welding process. J. Manuf. Process. 2015, 17, 48–57. [CrossRef]
6. Krishnan, S.; Dulkarni, D.V.; De, A. Pulsed current gas metal arc welding of P91 steels using metal cored
wires. J. Mater. Process. Technol. 2016, 229, 826–833. [CrossRef]
7. Kapal, P.; Surjya, K.P. Effect of pulse parameters on weld quality in pulsedgas metal arc welding: A review.
J. Mater. Eng. Perform. 2011, 20, 918–931.
8. Krishnan, S.; Dulkarni, D.V.; De, A. Multipass pulsed current gas metal arc welding of P91 steel. Sci. Technol.
Weld. Join. 2016, 21, 171–177. [CrossRef]
9. Sireesha, M.; Albert, S.K.; Sundaresan, S. Importance of filler materialchemistry for optimising weld metal
mechanical properties in modified 9Cr–1Mo steel. Sci. Technol. Weld. Join. 2001, 6, 247–254. [CrossRef]
10. Arivazhagan, B.; Sundaresan, S.; Kamaraj, M. A study on influence ofshielding gas composition on toughness
of flux-cored arc weld of modified9Cr–1Mo (P91) steel. J. Mater. Process. Technol. 2009, 209, 5245–5253.
[CrossRef]
11. Arivazhagan, B.; Kamaraj, M. Metal-cored arc welding process for joining of modified 9Cr-1Mo (P91) steel.
J. Manuf. Process. 2013, 15, 542–548. [CrossRef]
12. Shanmugarajan, B.; Padmanabham, G.; Kumar, H.; Albert, S.K.; Bhaduri, A.K. Autogenous laser welding
investigations on modified 9Cr–1Mo (P91) steel. Sci. Technol. Weld. Join. 2011, 16, 528–534. [CrossRef]
13. Kundu, A.; Bouchard, P.J.; Kumar, S.; Venkata, K.A.; Francis, J.A.; Paradowska, A.; Dey, G.K.; Truman, C.E.
Residual stresses in P91 steel electron beam welds. Sci. Technol. Weld. Join. 2013, 18, 70–75. [CrossRef]
14. Pai, A.; Sogaladc, I.; Albert, S.K.; Kumar, P.; Mitra, T.K.; Basavarajappa, S. Comparison of microstructure
& properties of modified 9Cr-1Mo welds produced by narrow gap hot wire & cold wire gas tungsten arc
welding processes. Procedia Mater. Sci. 2014, 5, 1482–1491.
15. El-Dosoky, O.E.; Abd El-Azim, M.E.; ElKossy, M.R. Analysis of creep behavior of welded joints of P91 steel
at 600 ◦ C. Int. J. Press. Vessel. Pip. 2019, 171, 145–152. [CrossRef]
16. Hyde, T.H.; Saber, M.; Suna, W. Creep crack growth data and prediction for a P91 weld at 650 ◦ C. Int. J. Press.
Vessel. Pip. 2010, 87, 721–729. [CrossRef]
17. Standard, A.S. Standard test method for measurement of creep crack growth rates in metals. In Annual Book
of ASTM Standards; ASTM: Philadelphia, PA, USA, 2001; Volume 3.
18. Kumar, Y.; Venugopal, S.; Sasikala, G.; Albert, S.K.; Bhaduri, A.K. Studyofcreepcrackgrowthinamodified
9Cr–1Mo steelweldmetal and heataffectedzone. Mater. Sci. Eng. A 2016, 655, 300–309. [CrossRef]
Metals 2020, 10, 99 22 of 23

19. Venugopal, S.; Sasikala, G.; Kumar, Y. Creep Crack Growth Behavior of a P91 Steel Weld. Procedia Eng. 2014,
86, 662–668. [CrossRef]
20. Baral, J.; Swaminathan, J.; Chakrabarti, D.; Ghosh, R.N. Effect of welding on creep damage evolution in P91B
steel. J. Nucl. Mater. 2017, 490, 333–343. [CrossRef]
21. Divya, M.; Das, C.R.; Albert, S.K.; Goyal, S.; Ganesh, P.; Kaul, R.; Swaminathan, J.; Murty, B.S.; Kukreja, L.M.;
Bhaduri, A.K. Influence of welding process on Type IV cracking behavior of P91 steel. Mater. Sci. Eng. A
2014, 613, 148–158. [CrossRef]
22. Wang, Y.; Li, L.; Kannan, R. Transition from Type IV to Type I Cracking in Heat-Treated Grade 91 Steel
Weldments. Mater. Sci. Eng. A 2018, 714, 1–13. [CrossRef]
23. Sharma, A.; Verma, D.K.; Kumaran, S. Effect of post weld heat treatment on microstructure and mechanical
properties of Hot Wire GTA welded joints of SA213 T91 steel. Mater. Today Proc. 2018, 5, 8049–8056.
[CrossRef]
24. Venkata, K.A.; Kumar, S.; Dey, H.C.; Smith, D.J.; Bouchard, P.J.; Truman, C.E. Study on the Effect of Post
Weld Heat Treatment Parameters on the Relaxation of Welding Residual Stresses in Electron Beam Welded
P91 Steel Plates. Procedia Eng. 2014, 86, 223–233. [CrossRef]
25. Paddea, S.; Francis, J.A.; Paradowskac, A.M.; Boucharda, P.J.; Shibli, I.A. Residual stress distributions in
a P91 steel-pipe girth weld before and after post weld heat treatment. Mater. Sci. Eng. A 2012, 534, 663–672.
[CrossRef]
26. Pandey, C.; Mahapatra, M.M.; Kumar, P.; Kumar, S. Effect of post weld heat treatments on microstructure
evolution and type IV cracking behavior of the P91 steel welds joint. J. Mater. Process. Technol. 2019, 166,
140–154. [CrossRef]
27. Pandey, C.; Mahapatra, M.M.; Kumar, P.; Sirohi, S. Fracture behaviour of crept P91 welded sample for
different post weld heat treatments condition. Eng. Fail. Anal. 2019, 95, 18–29. [CrossRef]
28. Pandey, C.; Mahapatra, M.M.; Kumar, P.; Saini, N.; Srivastava, A. Microstructure and mechanical property
relationship for differentheat treatment and hydrogen level in multi-pass welded P91 steeljoint. J. Manuf.
Process. 2017, 28, 220–234. [CrossRef]
29. Pandey, C.; Mahapatra, M.M.; Kumar, P.; Saini, N.; Thakre, J.G.; Vidyarthy, R.S.; Narang, H.K. A brief study
on d-ferrite evolution in dissimilar P91 and P92 steel weld joint and their effect on mechanical properties.
Arch. Civ. Mech. Eng. 2018, 18, 713–722. [CrossRef]
30. Widak, V.; Dafferner, B.; Heger, S.; Rieth, M. Investigations of dissimilar welds of the high temperature steels
P91and PM2000. Fusion Eng. Des. 2013, 88, 2539–2542. [CrossRef]
31. Akram, J.; Kalvala, P.R.; Misra, M.; Charit, I. Creep behavior of dissimilar metal weld joints between P91 and
AISI 304. Mater. Sci. Eng. A 2017, 688, 396–406. [CrossRef]
32. Vidyarthy, R.S.; Kulkarni, A.; Dwivedi, D.K. Study of microstructure and mechanical property relationships
of A-TIG welded P91-316L dissimilar steel joint. Mater. Sci. Eng. A 2017, 695, 249–257. [CrossRef]
33. Welding—Fusion-Welded Joints in Steel, Nickel, Titanium and Their Alloys (Beam Welding Excluded)—Quality
Levels for Imperfections; ISO 5817; International Organization for Standardization: Geneva, Switzerland, 2014.
34. Metallic Materials—Conversion of Hardness Values; ISO 18265; International Organization for Standardization:
Geneva, Switzerland, 2013.
35. Non-Destructive Testing of Welds—Visual Testing of Fusion-Welded Joints; ISO 17637; International Organization
for Standardization: Geneva, Switzerland, 2003.
36. Non-Destructive Testing—Penetrant Testing—Part 1: General Principles; ISO 3452-1; International Organization
for Standardization: Geneva, Switzerland, 2013.
37. Process Piping; ASME B31.3; The American Society of Mechanical Engineers: New York, NY, USA, 2010.
38. Newell, W.F. Guideline for Welding P(T) 91; Euroweld, Ltd.: Mooresville, NC, USA,
2001; Available online: http://cfs9.blog.daum.net/upload_control/download.blog?fhandle=
MEZMejdAZnM5LmJsb2cuZGF1bS5uZXQ6L0lNQUdFLzAvMjQuUERG&filename=24.PDF&filename=
Guideline+for+Welding+P91.PDF (accessed on 16 December 2019).
39. Metallic Materials—Vickers Hardness Test—Part. 1: Test. Method; ISO 6507-1; International Organization for
Standardization: Geneva, Switzerland, 2018.
40. Destructive Test on Welds in Metallic Materials—Macroscopic and Microscopic Examination of Welds; BS EN 1321;
British Standards Institution: London, UK, 1997.
Metals 2020, 10, 99 23 of 23

41. ASME. ASME Boiler and Pressure Vessel Code An International Code—Qualification Standard for Welding, Brazing,
and Fusing Procedures; Welders; Brazers; and Welding, Brazing, and Fusing Operators; IX: 2015, QW 150; The
American Society of Mechanical Engineers: New York, NY, USA, 2015.
42. Metallic Materials—Tensile Testing—Part 2: Method of Test at Elevated Temperature; ISO 6892-2; International
Organization for Standardization: Geneva, Switzerland, 2018.
43. ASME. Boiler and Pressure Vessel Code An. International Code—Qualification Standard for Welding, Brazing, and
Fusing Procedures; Welders; Brazers; and Welding, Brazing, and Fusing Operators; IX: 2015, QW 163; The American
Society of Mechanical Engineers: New York, NY, USA, 2015.

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