SPE-176488-MS

Corrosion Assessment of Different Production Casings and Material

Selection in Sour Gas Wells
Zeng Dezhi and Zhang Naiyan, Southwest Petroleum University; Wang Feng, Research Institute of Natural Gas
Technology; Chen Rui, Sichuan Kehong Petroleum Engineering Co., Ltd; LI Tianlei, China Petroleum
Engineering Co., Ltd; Ren Chengqiang, Hu Junying, and Shi Taihe, Southwest Petroleum University

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/IATMI Asia Pacific Oil & Gas Conference and Exhibition held in Nusa Dua, Bali, Indonesia, 20 –22 October 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
In order to assess the applicability of three steel specimens (T95, 110SS-2Cr and 825 steel) in sour gas
well, corrosion tests were conducted in a simulated gas field solution containing both 0.55MPa H2S and
0.75MPa CO2 at 55 °C-100 °C for 72h in an autoclave. Then the corresponding corrosion products were
analyzed and compared through EDS and SEM technologies. The stress corrosion cracking (SCC)
behavior of three steel specimens had been tested using four point bending (FPB) technique and
constant-load test. The results showed that the 825 steel had lowest corrosion rate among all those steels.
The corrosion rate of T95 steel was higher than 110SS-2Cr steel for its looser corrosion products. With
the increase of temperature, T95 steel and 110SS-2Cr steel corrosion product film thickened, and the
trends of crystallization and agglomeration were clear. The main components of the film were FexSy,
FeCO3 and compounds containing a small amount of Cr. It could also be found that the Cr content of
110SS-2Cr steel corrosion products was higher than that of T95 steel, which may contribute to its lower
corrosion rate. According to the FPB results, all of those three steels did not get broken under 85% stress
state in the simulated field condition. The constant load tests also showed that under 72% stress state, the
T95 steel and 110SS-2Cr steel were not broken, indicating a good resistance to environmental cracking
with low stress corrosion sensitivity. As a result, the 825 steel could be used below the packer of
production casing; the 110SS-2Cr steel is appropriate to be used in the middle of production casing; the
T95 steel is suitable for the wellhead of production casing.

Introduction
Nowadays, in order to meet the world-wide energy demand, the exploitation of sour oil and gas fields has
been developed. And the search for new sources of oil and gas has pushed the operational activities to
harsher environment[1].thereby the subsequent production casing failures have been one of great concerns
in the production and transportation of sour oil and gas. Several previous studies have shown that Incoloy
825 alloy was designed to resist various corrosive environments, especially in sulfuric and phosphoric acid
environments and can be widely used in sea water or even sour gas and oil wells [2–3].
2 SPE-176488-MS

However, taking account of high production cost of 825 steel and economic profits, it was limited in
the production and application of oil and gas field. As the technologies of metallurgy and microalloying
develop, the newly discovered low Cr containing alloy has been activately researched[4–7]. 110SS-2Cr
steel is typical low Cr containing alloy of Oil Country Tubular Goods(OCTG). Wu et al[8] found that, for
lower Cr containing steel, the formation of a compact and self-repairable Cr-rich scale increases the
corrosion resistance, and thus decreasing the risk of localized corrosion. However, based on the ISO
11960 standard[9], not all 110ksi steel is suitable for sour (hydrogen sulfide-containing) service applica-
tions. 110SS-2Cr steel, as one of common OCTG, is not defined as sulfur-resistance steel by the relevant
standards. Although T95 steel has been stipulated as one of anti-SSCC casings by API SPEC 5CT[10], the
strength of T95 steel cannot meet the demands of oil industry as the well depth increases. The material
selection of three steels(825, T95 and 110SS-2Cr) in H2S/CO2 environment has not been systematically
compared and researched.
In the present work, the stress corrosion cracking performance and weight loss corrosion on three steels
at different temperatures were investigated in stimulated H2S/CO2 containing gas field solution, and the
corrosion morphology and characteristics were also studied. In addition, the corrosion mechanism was
also proposed and discussed. The results will provide theoretical reference for the material selection and
application of production casing in high sour oil and gas field.
Methodology and experimental
Materials and specimen preparation
According to the ASTM standards, the three steel coupons (T95, 110SS-2Cr and 825 steel) were
prepared with dimension of 106 mm ⫻ 15mm ⫻ 2.8mm and 30 mm ⫻ 15 mm ⫻ 3 mm. These samples
were used for four point bending test and dynamic high temperature (HT) autoclave experiments
respectively. In addition, Subsize constant load test specimens with an outside diameter of 3.81mm were
used to perform this CL test according to NACE TM0177-2005 standard[11], as shown in Fig.1.The
chemical composition of the samples and the stimulated gas field solution are listed in Table1 and Table2.

Figure 1—Dimension of standard constant load test specimens

Table 1—Chemical composition of three steel (wt %)

Element C Si Mn P S Ni Cr Mo Ti V Cu Al

T95 0.304 0.215 0.52 0.014 0.008 0.009 0.99 0.173 - 0.007 0.044 0.022
110SS-2Cr 0.318 0.343 0.59 0.014 0.005 0.067 2.42 0.85 - 0.076 0.036 0.061
825 0.05 0.5 1.0 0.014 0.03 38 20 2.5 0.8 - 1.5 0.15
SPE-176488-MS 3

Table 2—Chemical composition of the stimulated gas field solution (g/L)

Formula NaCl KCl MgCl2·6H2O CaCl2 NaHCO3 Na2SO4

Content 148.37 19.2 20.35 31.7 0.978 1.05

Anti-SCC performance evaluation experiments

To determine the stress corrosion cracking performance, Four Point Bending(FPB) testing and constant
load(CL) testing in accordance with NACE TM 0177-2005 standard[11] were adopted as methods for
conducting this corrosion evaluation process.
The four point bending specimens extracted from the parent mental were loaded at a 85% stress level.
The specific loading model is given in Fig.2. After loading, the specimens fixed in special fixture were
placed in the self-designed high temperature (HT) autoclave. Then the deaerated stimulated gas field
solution had been used with total pressure 30MPa, partial pressure of 0.75MPa CO2 and 0.55MPa H2S.
The test period was 720h with average temperature at 100 °C.

Figure 2—the loading schematic of four point bending test

Casing steels of T95 and 110SS-2Cr with three parallel samples were evaluated using the constant load
test method. Before testing, specimens shall be degreased with solvent and rinsed with acetone, and the
gauge section of test specimen shall not be contaminated after cleaning. Constant load test was conducted
with proof ring device. Then all specimens were loaded at a 72% stress state and immersed in NACE A
solution saturated with H2S to subject to a severe corrosion process with test period 720h at 24 °C after
testing, the surface of the gauge section of test specimens shall be cleaned and inspected for evidence of
cracking.

Dynamic HT autoclave experiment

The three samples of 825, T95 and 110SS-2Cr steel were polished to a mirror finish in order to
eliminate scratches, and then cleaned by mineral ether and anhydrous ethanol, finally dried and weighed.
The coupons were placed in the high temperature (HT) autoclave, and the oxygen free simulant gas field
solution was poured into it. Simultaneously, autoclave was quickly sealed and pure N2 was used to test
pressure. While heating to the experimental temperature, 0.55MPa standard H2S and 0.75MPa CO2 gases
were delivered into the HT autoclave that made from C276 nickle-based alloy and the flow rate was then
set to 1 m/s to start the experiment, these samples were used to perform a corrosion process at different
temperatures(50, 80and 100 °C) for 72h.
After performing the weight-loss tests, the corrosion products of the specimens were investigated by
scanning electron microscopy (SEM) and energy dispersive X-Ray spectroscopy (EDX).
4 SPE-176488-MS

Results and Disscussion

Stress corrosion evaluation
Table.3 shows the results of four point bending specimens after 720h test. It can be found obviously that
all of those three steels do not get broken under 85% stress state in the simulated gas field condition,
indicating a good resistance to environmental cracking with low stress corrosion susceptibility.

Table 3—Evaluation results of four point bend test

Steel Test conditions Solution Results

825 Four point bend specimen, 85% X gas field simulation water 720NF
110SS-2Cr ␴S 100°C, PH2S⫽ 0.55MPa, 720NF
PCO2⫽ 0.75MPa Total
T95 720NF
pressure⫽30 MPa

Evaluation results of constant load (CL) test under normal temperature and pressure are summarized
in Table 4.From Table 4, we can see that both T95 and 110SS-2Cr have good anti-sulfur performance at
the 72% loading stress state and have passed the CL corrosion test.

Table 4 —Evaluation results of constant load test

Material Loading stress (MPa) Loading displacement (mm) Results

T95 72%␴s 0.9334 NF

T95 72%␴s 0.9456 NF
T95 72%␴s 0.9471 NF
110SS-2Cr 72%␴s 1.0695 NF
110SS-2Cr 72%␴s 1.0737 NF
110SS-2Cr 72%␴s 1.0783 NF

Analysis of weight–loss test

Each coupon was weighed before and after immersion and the change in weight from material lost over
time was used to calculate the rate of uniform corrosion from weight loss using the following equation:

Where v is the corrosion rate (mm/a), ⌬m is the weight loss (g), ␳ is the density of steel (g/cm3), A
is the surface area (cm2), ⌬t is the erosion time (h).
The Contrastive Analysis results of corrosion rate on three different steels (T95, 110SS-2Cr and 825
steel) are specifically demonstrated in Table 5 and Fig.3.

Table 5—Average corrosion rate of three materials under different temperatures (mm/a)
Corrosion rate (mm/a)

Material 55 °C 80 °C 100 °C

825 0.0082 0.0228 0.0209

110SS-2Cr 0.0391 0.0897 0.0974
T95 0.0502 0.1038 0.1247
SPE-176488-MS 5

Figure 3—Average corrosion rate of three materials under different temperatures

As shown in Fig.3, the corrosion rates of T95 and 110SS-2Cr increased with the rise in temperature,
and then reached the maximum at 100 °C whereas there was no significant difference among the corrosion
rates of 825 steel in the stimulated gas solution within the temperature range studied (55°C-100°C). In
addition, No over 0.025mm/a was found in the corrosion rate of 825 steel (as is shown in Table 5).
According to NACE RP0775-05 standard[12], it is in the range of slight corrosion, while that of another
two low alloy carbon steels (T95 and 110SS-2Cr) are moderate for its corrosion rate ranging from
0.025mm/a to 0.125mm/a.

Microanalysis of corrosion scales

Temperature, one of the most important factors influencing H2S/CO2 corrosion, mainly affected the
corrosion performance by increasing chemical reaction rate and influencing the generation and status of
the corrosion scales[13–14].
To figure out the effect of temperature on the corrosion product of the three steels, the surface
morphologies of corrosion scales on three steels were studied by scanning electron microscopy (SEM).
And the corresponding compositions were evaluated by EDX analysis technology. the corrosion rate of
825 steel at 80 °C looked almost identical to that at 100 °C, therefore, hence the morphologies and
compositions on 825 steel at 80 °C were analyzed emphatically. Fig.4 shows the SEM surface morphol-
ogies of corrosion scales on 825 steel at 55 °C and 80 °C. And the corresponding EDS results of corrosion
products are listed in Table 6.

Figure 4 —SEM micrographs of 825 steel corrosion at 55°C and 80°C

6 SPE-176488-MS

Table 6 —The EDS results of 825 steel corrosion products (At%)

Material T/°C C O S Cr Ni Fe

825 55 7.02 9.19 4.13 23.6 34.56 28.52

80 14.17 19.6 3.66 16.18 23.21 20.16

It can be found in Fig.4 that the polished lines of raw 825 steel (nearly 2000 magnification times),
which can be clearly seen, indicated mild corrosion. The results (Table. 6) demonstrated that the elements
of 825 steel such as Fe, S and C appeared in the survey spectrum of the corrosion scale surface. And yet,
rare elements such as Cr and Ni occurred in the corrosion product of 825 steels which may be responsible
for its low corrosion rate. In addition, through the experimental research of corrosion behavior on Ni-base
alloy steel in H2S/CO2 environments, zhao et al[15] asserted that two passivation layers occurred on the
surface of Ni-base alloy steel the outer corrosion scale is mainly composed of metal sulfides(NiS),and
inner layer by NiS and Ni,Cr and mental oxides(CrO3).According to the bipolar passivation film theory
in a study conducted by sato, the passivation film contains two layers, the outer layer prevents the inward
diffusion of corrosive ions, moreover, the inner layer stops metal ions spreading outside the Passivation
membrane, and they interact with each other to better protect metal matrix[16]. Meanwhile, a very small
amount of element sulphur was observed on the corrosion scale surface in Fig.4 and Cr2S3 may be
produced, thus indicating mental substrate has been subjected to corrosion. Despite all this, the bipolar
structure of passivation film has not yet been damaged due to its self—repairing capacity, thus resulting
in good anti-corrosion performance.
The SEM surface morphologies of corrosion scales of 110SS-2Cr and T95 steel at different temper-
atures are given in Fig.5 and Fig.6, respectively. As can be observed from Fig.6a and Fig.7a that
110SS-2Cr and T95 steel have formed complete and continuous corrosion product films at 55 °C, which
may effectively decrease the quantity of corrosion medium that took part in the electrochemical reaction.
Therefore, 110SS-2Cr and T95 steel have the lower corrosion rates at 55 °C, which corresponds with
Table 5. With the increase of temperature, corrosion product films of T95 and 110SS-2Cr steel thickened
and the trends of crystallization and agglomeration were clear. Then the space between crystals and blocks
increased, and metal-matrix would be activated, resulting in galvanic corrosion caused by corrosion scales
and mental matrix, which intensified the localized corrosion and increased the corrosion rate.

Figure 5—SEM micrographs of 110SS-2Cr steel at different temperatures

SPE-176488-MS 7

Figure 6 —SEM micrographs of T95 steel at at different temperatures

Compare Fig.5a with Fig.6a, Crystal size of 110SS-2Cr steel was smaller and denser than that of T95
steel at 55 °C. Besides, the corrosion scales of 110SS-2Cr steel were compactly packed at 80 °C, while
those of T95 steel were relatively loose. Severe corrosion cracks also can be discovered in T95 steel at
100 °C. Hence the corrosion rate of T95 steel was higher than that of 110SS-2Cr.
Table 7 shows the EDS results of corrosion products of T95 steel and 110SS-2Cr steel at different
temperatures. The results indicated that the principal components of corrosion products on two low alloy
carbon steels were mainly FexSy and FeCO3 as well as a certain amount of Cr compounds. In addition,
Compared with T95 steel, more chromium element existed in the corrosion scales of 110SS-2Cr.
Combined with Table 1, 110SS-2Cr steel contains higher content of chromium element that can help
increasing the tensile strength and forming a passivation film of better stability than T95 steel. That’s the
very reason why 110SS-2Cr steel has lower corrosion rate and better anti-corrosion performance. Previous
study[17] have also shown that the corrosion scale over the surface of 2Cr steel has a two-layer structure,
and the amorphous inner scale of 2% Cr steel mainly consists of FeCO3 and Cr(OH)3, the outer scale is
mainly made up of FeCO3 in the form of crystal, both two layers have come together to inhibit the
corrosion. Additionally, through the study on corrosion behavior of 3% Cr steel in CO2 environments, zhu
et al[18] pointed out that the addition of Cr to steel can cause spontaneous prepassivation, which
simultaneously affected the cathodic and anodic processes.

Table 7—The EDS results of T95 steel and 110SS-2Cr steel (At%)
Material T/°C C O S Cr Fe

55 11.74 38.60 9.79 1.33 25.92

110SS-2Cr 80 12.27 39.07 6.24 1.28 33.42
100 14.97 27.91 5.99 1.16 40.04
55 17.27 23.93 13.89 0.61 33.60
T95 80 15.08 20.19 6.48 0.92 33.68
100 14.74 11.80 7.12 1.07 64.01

Material selection discussions

825 steel is one kind of high-nickel alloy( Table.1 38%Ni), and the uniform corrosion rate of 825 steel
is much lower than that of T95 steel and 110SS-2Cr steel at 100 °C, indicating its better anti-corrosion
and high temperature resistance performance. However, due to its expensive cost, the 825 steel could be
used below the packer of production casing.
Compared with T95 steel, the stress corrosion cracking (SCC) susceptibility of 110SS-2Cr steel is
much higher at wellhead depth with temperatures below 55°C. Therefore, it’s inadvisable to apply the
8 SPE-176488-MS

110SS-2Cr at wellhead. In addition, the uniform corrosion rate of T95 steel is also low than 0.076mm/a,
which conforms the standards for corrosion prevention in oil and gas field. Considering the above, the T95
steel is suitable for the wellhead of production casing.
110SS-2Cr steel, as one of high-strength steels, whose Cr-containing corrosion products prevent anions
diffusing into corrosion products, thus decreases the corrosion rate. From figure 2, when temperature
increases from 55 °C to 100 °C, the uniform corrosion rate of 110SS-2Cr steel is a bit lower than that of
T95 steel. Besides, due to its poor SSCC resistance performance, hence, 110SS-2Cr steel is suggested to
apply in the middle of production casing.
Although the material selection result is in accordance with the criterion for security and economics,
galvanic corrosion will be the critical problem and needs to be further studied.

Conclusion
Conclusions can be drawn as follows:
1. The FPB results demonstrated that all of those three steels did not get broken under 85% stress
state in the simulated field condition. The constant load tests also showed that under 72% stress
state, the T95 steel and 110SS-2Cr steel were not broken, indicating a good resistance to
environmental cracking with low stress corrosion sensitivity.
2. Indoor weight loss tests showed that the 825 steel had lowest corrosion rate among all those steels.
The corrosion rate of T95 steel was higher than 110SS-2Cr steel for its looser corrosion products.
With the increase of temperature, T95 steel and 110SS-2Cr steel corrosion product film thickened,
and the trends of crystallization and agglomeration were clear. The main components of the film
were FexSy, FeCO3 and compounds containing a small amount of Cr. It could also be found that
the Cr content of 110SS-2Cr steel corrosion products was higher than that of T95 steel, which may
contribute to its lower corrosion rate.
3. The 825 steel could be used below the packer of production casing; the 110SS-2Cr steel is
appropriate to be used in the middle of production casing; the T95 steel is suitable for the wellhead
of production casing.

Acknowledgments
The authors acknowledge the support from the National Nature Science Foundation project of china (No.
51374177) and the youth backbone teachers support program of Southwest Petroleum University.

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