NACE Paper No.

MECCOCT18-12633

Hydrophobic-Autocatalytic Nickel Coatings for

Downhole Corrosion and Scale Mitigation of Sour Gas Condensate Wells

Yahya T. Al-Janabi Abduljalil H. Al-Rasheed

Saudi Aramco Saudi Aramco
Research and Development Center Research and Development Center
Dhahran 31311 Dhahran 31311
Saudi Arabia Saudi Arabia

Ali A. Jabran Hameed H. Al-Badairy

Saudi Aramco Saudi Aramco
Research and Development Center Research and Development Center
Dhahran 31311 Dhahran 31311
Saudi Arabia Saudi Arabia

Moayyad N. Alneemai Qiwei Wang

Saudi Aramco Saudi Aramco
Research and Development Center Research and Development Center
Dhahran 31311 Dhahran 31311
Saudi Arabia Saudi Arabia

Tao Chen Tawfiq A. Al-Shafai

Saudi Aramco Saudi Aramco
EXPEC Advanced Research Center Research and Development Center
Dhahran 31311 Dhahran 31311
Saudi Arabia Saudi Arabia

Fakuen F. Chang Nada F. Qari

Saudi Aramco Saudi Aramco
EXPEC Advanced Research Center Research and Development Center
Dhahran 31311 Dhahran 31311
Saudi Arabia Saudi Arabia
 ABSTRACT

Several hydrophobic-autocatalytic (electroless) nickel coating systems were studied for the protection of
downhole casings and tubing against both corrosion and scaling in sour gas wells. Nine (9) nickel-based
coating systems were examined in this study where the total number of samples analysed was twenty
nine (29). The methods used to study these samples included optical microscopy, scanning electron
microscopy (SEM), contact angle measurements, and electrochemical impedance spectroscopy (EIS).
These analyses were performed before and after the test samples were exposed to the downhole
conditions of a typical sour gas well.

Sour gas wells are characterized by the presence of the corrosive acid gas hydrogen sulfide (H2S), which
attacks the surfaces of carbon steel tubing and casings to produce different forms of iron sulfide (FeS)
films or scales. These films can grow in size causing blockage which is a major concern in sour gas wells.
Removal of these films by chemical or mechanical means has been very challenging. Preventing their
formation and/or growth by applying hydrophobic-autocatalytic nickel-based coatings on the internal
surfaces could be more cost-effective. These coatings were selected for two critical features: the
impregnated nickel in the coating film would provide the corrosion resistance; while hydrophobicity would
prevent adhesion of the iron sulfide and other mineral scales.

The hydrophobic-autocatalytic (electroless) nickel coating systems were formulated by varying several
parameters like the alloying element(s) besides nickel, the hydrophobicity-inducing materials, the
particles loading, and the pre-treatment procedure. The coating films were prepared with three
thicknesses: 0.0005”, 0.001”, and 0.004”. The base metal used is carbon steel T 95, which is generally
specified for sour gas condensate wells. The SEM images revealed various degrees of porosity and
surface definition which varies from crystal-like grown surfaces to amorphous morphologies. The contact
angles measured ranged from 71° to 104°. According to EIS data, the measured total impedance value
at low frequency were in the order of magnitude of 105 ohm. In this paper, the results of these coatings
will be presented and discussed based on their performance under simulated sour gas wells’ downhole
conditions.

Key Words: autocatalytic nickel coating, electroless nickel coating, hydrophobic coating, sour gas wells,
downhole corrosion, downhole scaling

INTRODUCTION
Sour gas wells are characterized by the presence of the corrosive acid gas hydrogen sulfide (H2S), which
attacks the surfaces of carbon steel tubing and casings to produce different forms of iron sulfide (FeS)
films or scales. These films can grow in size causing blockage, which is a major concern in sour gas
wells. Removal of these films by chemical or mechanical means has been very challenging. Preventing
their formation and/or growth by applying hydrophobic-autocatalytic nickel-based coatings on the internal
surfaces might be more cost-effective. Developing effective coated materials can significantly mitigate
corrosion induced iron sulfide issues and improve the treatment efficiency.
Nickel-based coatings were selected for two critical features: the impregnated nickel in the coating film
would provide the corrosion resistance; while hydrophobicity would prevent adhesion of the iron sulfide
films. These nickel coating systems were formulated by varying several parameters like the alloying
element(s) besides nickel, the hydrophobicity-inducing materials, the particles loading, and the
pretreatment procedure. The coatings and samples were prepared by an external collaborator. The
coating films were prepared with three thicknesses: 0.0005”, 0.001”, and 0.004”. The base metal used
was carbon steel T 95, which is generally specified for sour condensate wells. The coatings were applied
using the electroless nickel plating (ENP) method.
The objective of this study was to evaluate the performance of these test panels, which were coated with
different coatings formulations, in preventing corrosion and corrosion-induced iron sulfide deposition,
typically found in sour gas-fields in the presence of H2S and CO2.

EXPERIMENTAL PROCEDURE
Several advanced laboratory methods have been used to study the characteristics of hydrophobic-
autocatalytic (electroless) nickel coating systems. These systems are targeted for the protection of
downhole casings and tubing against both corrosion and scaling in sour gas wells. Nine (9) nickel-based
coating systems were examined in this study where the total number of samples analyzed was twenty
nine (29). The metal specimens were cut from a T-95 downhole tubular with dimensions 2.875 x 0.875 x
0.125 inches. The results for six (6) of the twenty nine (29) coated panels will be presented and discussed
here. The methods used to study these samples included optical microscopy, scanning electron
microscopy (SEM), contact angle measurements, and electrochemical impedance spectroscopy (EIS).
These analyses were repeated after the test samples were exposed to the downhole conditions of a
typical sour gas well.
Following are the autoclave test parameters used to simulate downhole conditions of a typical sour gas
well:

• Water/hydrocarbon/gas
• Autoclave test temperature: 160 °C (320 °F)
• Autoclave test pressure: ~5000 psi
• Gas phase content: 8% H2S; 4% CO2; Balance N2
• Chloride ion: 150,000 ppm
• Tubing material: Low alloy API 5CT T-95 carbon steel (Figure 1)
• Test duration: 18 hours
• Rapid decompression from 5000 to ambient psi in 5 minutes
• Static test conditions

Following are the liquids’ compositions:

• Formation water brine composition (mg/l):

• Cl– : 150,000
• Ca 2+
: 23,000
• Mg2+ : 2,500
• HCO3– : 325
• Na+ : 66,300
• Hydrocarbon phase: Kerosene

The coated test panels were placed in a glass jar filled with the test solution and the hydrocarbon phase.
The levels of these phases were controlled in such a way to expose the test panels to the three phases:
aqueous, hydrocarbon, and gas, Figure 1.
 a) Pipe spool

b) Before exposure c) After exposure

Figure 1: Photographs of the pipe spool (a) used to machine the test panels, and the coated panels
test assembly before (b) and after (c) exposure to the test conditions simulating downhole gas
wells.

The test panels’ assembly was placed inside an autoclave, Figure 2. A 10kpsi/4L autoclave reactor was
used to conduct the corrosion tests under simulated downhole gas wells conditions. The reactor is
constructed from C-276 (UNS N10276) alloy making it capable to withstand harsh corrosive
environments. After the test panels’ assembly was placed inside the autoclave, the vessel was sealed
and all necessary connections were made ready to start the test. Oxygen was removed by evacuating
the autoclave chamber which was then pressurized with H2S followed by CO2 and N2 gas. The initial
partial pressures at room temperature were calculated using the ideal gas law. The system was then
heated to the target temperature of 160°C and the pressure was noted, which was around 5000 psig.
After 18 hours, the pressure was released quickly to test for the effect of rapid decompression. This was
a screening test and, therefore, was conducted under static conditions. The plan was to conduct a
dynamic test for the coating systems, which show acceptable performance. Also shown in Figure 1 is the
test panels’ assembly after completing the test and after removal from the autoclave.
Figure 2: Photograph of the 10kpsi/4L autoclave reactor used in this study to simulate gas wells’
downhole conditions.

Environmental Scanning Electron Microscopy /Energy Dispersive X-ray (ESEM/EDX) and Stereo
Microscope Analysis
The field emission gun-environmental scanning electron microscope (FEG-ESEM) was utilized to study
topographical and compositional features of the failed coating sample. To determine the elemental
chemical composition, the energy dispersive X-ray detector (EDX) attached to the ESEM was used. The
samples were analyzed using FEI Quanta 400 ESEM. The ESEM was operated at 10-15 kV, and 10 mm
working distance. Topographical secondary electron and compositional backscattered images at different
magnifications together with EDS X-ray spectra were acquired from different areas of the examined
sample. For optical microscopy, a Leica EZ4 Stereo Microscope was used with 8× - 35× magnifications.
The sample was mounted without any surface preparation.

Electrochemical Impedance Spectroscopy (EIS) Measurements

EIS measurements were conducted using a three-electrode electrochemical cell arrangement; a standard
flat cell manufactured by EG&G, Figure 3. The reference electrode (RE) is a standard saturated calomel
electrode (SCE). The counter electrode (CE) is a platinum mesh. The working electrode (WE) lead wire
was connected to the test panel by scraping a small portion of the coating at the edge, which was painted
with highly corrosion resistant fusion bonded epoxy (FEB) afterwards. The test panels were mounted on
the flat cell which was filled with 3.5 wt.% NaCl. The lead wires from the EIS instruments were connected
to the RE, CE, and WE. EIS measurements were then performed at ambient temperature using an EG&G
Potentiostat 283/ FRA 1025. The perturbation amplitude was kept constant at ±10mV. The frequency
range was 0.1 Hz through 100 kHz. The EIS measurement area was a 2” diameter circle. After exposure,
the EIS measurements were conducted on the lower part immersed in the water phase during the testing
under downhole conditions.
 Pt Counter Electrode
Calomel Reference
Electrode

PE Sample Panel

Working Electrode

Figure 3: A photograph of the EG&G standard flat electrochemical cell used for evaluation of the
polyethylene (PE) coating. A 3-electrode arrangement was used for Electrochemical Impedance
Spectroscopy (EIS) measurements.

RESULTS AND DISCUSSION

The results of six test panels will be presented here and these are Panels # 3, 5, 6, 8, 12, and 14, shown
in Figure 4 before and after exposure. The surface areas exposed to water, kerosene, and gas can be
distinguished in these panels, especially Panels # 12 and 14. All of these panels were pretreated in the
same way with a first layer of a 0.001” (~25 microns, µ) thickness high phosphorus ENP (electroless
nickel plating) followed by the application of a second layer containing added particles. Panels # 3, 8,
and 12 were also heat treated at 350°C. Black corrosion films, typical of iron sulfides, were observed on
all six panels as can be seen from the photographs after exposure. The stand used to hold the test
panels is made of PEEK and Hastelloy C-276, which exclude it from participating in the corrosion
reactions.
a) Before exposure

b) After exposure

Figure 4: Photographs of Panels # 3, 5, 6, 8, 12, & 14 before (a) and after (b) exposure to downhole
conditions. The three regions distributed vertically, which can be seen clearly on Panels # 12 &
14, are for the aqueous, hydrocarbon, and gas phases.

Figure 5 shows the optical photographs at 10× magnification of these six panels before and after
exposure. As can be seen from the photographs of the panels before exposure, the profiles of the metallic
substrates are apparent at the coating film thickness of 25 µ. The panels’ photographs after exposure
clearly indicate that corrosion attack took place, which is evident from the formation of corrosion films on
the surfaces of these panels. The inserts also give examples of damaged films by blister formation.
a) Before exposure

b) After exposure
Figure 5: Optical photographs of Panels # 3, 5, 6, 8, 12, & 14, at 10× before (a) and after (b)
exposure to downhole conditions. The areas shown in the photographs after exposure are at the
hydrocarbon/ aqueous interface, where the aqueous phase is on the right, and the hydrocarbon
phase is on the left. Photographs showing blistered films are also included as inserts.

The SEM images show variations in the surface structures of these coatings, Figure 6. The SEM image
for Panel #3 shows the unique surface microstructure of the Ni-B crystals, micorspheroids, which
becomes clear at 10,000×. The coating film in this case was not loaded with any particles. The SEM
image for Panel #5 shows the amorphous phase of polytetrafluoroethylene (PTFE). The coating film here
was loaded with a medium percentage of particles. The coating film on Panel #6 contains boron and
nitrogen. The cubic boron nitride crystals are visible at 10,000×. For Panels # 8, 12, and 14, the materials
added to the Ni-P coating were Talc, diamond, and SiC, respectively. These particles are visible in the
respective SEM images.

Figure 6: SEM images of Panels # 3, 5, 6, 8, 12, & 14. Magnifications are 10,000× and 500× for
inserts.

A hydrophobic coating1 should exhibit a contact angle (CA) of > 110o. The CA’s measured for these
panels are given in Table 1, and the corresponding pictures are shown in Figure 7. The CA’s correlate
with the surface morphology which is influenced by the filling materials, the loading, and the heat
treatment. The highest contact angle was measured for Panel #5, where PTFE filling is behind the
relatively higher hydrophobicity. The Talc filler in Panel #8 gave the lowest hydrophobicity among these
six test panels. The Ni-B and the diamond fillers were next, followed by BN and SiC filler materials.
Following is the sequence in terms of hydrophobicity based on contact angles starting with the highest:
PTFE> SiC> BN> diamond> Ni-B> Talc or #5 > #14 > #6 > #12 > #3 > #8. The first three were not heat-
treated. Heat treatment usually induce crystal growth and these surface irregularities normally reduces
hydrophobicity.
 TABLE 1
The Mean Contact Angles (CA) for Panels # 3, 5, 6, 8, 12, & 14
Panel # 3 5 6 8 12 14

CA mean [°] 73 ± 6 104 ± 2 95 ± 5 71 ± 1 78 ± 3 97 ± 4

Figure 7: Contact angle images of Panels # 3, 5, 6, 8, 12, & 14.

The EIS results before and after exposure are shown in Figure 8 using the Bode representation. Normally,
a measured total impedance value, |Z|, of 1×108 ohms or higher indicates an acceptable corrosion
protectiveness provided by the coating system2. For example, |Z| for StreaMaxTM is in the order of 1011
ohms3. StreaMaxTM is a fluoropolymer-based coating system developed by DuPontTM for downhole
production tubes for oil and gas wells4.
For the six panels discussed in this paper, all coating films gave |Z| values in the range of 5×104 ohms to
1×105 ohms, which are lower than the threshold value of 1×108 ohms. Upon exposure, |Z| dropped even
further to smaller values in the range of 2×102 ohms to 1×103 ohms. The impedance of the lower portion
of the exposed panels was measured, which corresponds to the area immersed in the aqueous solution
during the autoclave exposure. Based on the initial impedance values, these coating systems are not
expected to provide sufficient corrosion protection. The drop in impedance values after exposure
supports this observation.
The initial impedance values of these six panels were of the same order of magnitude. For all six samples,
the first layer (underlayer) was the same, i.e., high phosphorus ENP. They were loaded with different
particles or none in the case of #3. These similarities in the initial |Z| values indicate that the underlayer
was the main contributor to the observed overall impedance of the coating system. The same observation
holds for the impedance values measured after exposure to the downhole test conditions.
 1.E+06 1.E+06

1.E+05 Panel # 3 Before Exposure 1.E+05 Panel # 5 Before Exposure

Panel # 3 After Exposure Panel # 5 After Exposure

1.E+04 1.E+04
|Z| (Ohms)

|Z| (Ohms)
1.E+03 1.E+03

1.E+02 1.E+02

1.E+01 1.E+01

1.E+00 1.E+00
0.1 1 10 100 1000 10000 100000 0.1 1 10 100 1000 10000 100000
Frequency (Hz) Frequency (Hz)

1.E+06 1.E+06

Panel # 6 Before Exposure Panel # 8 Before Exposure

1.E+05 1.E+05
Panel # 6 After Exposure Panel # 8 After Exposure

1.E+04 1.E+04
|Z| (Ohms)

|Z| (Ohms)

1.E+03 1.E+03

1.E+02 1.E+02

1.E+01 1.E+01

1.E+00 1.E+00
0.1 1 10 100 1000 10000 100000 0.1 1 10 100 1000 10000 100000
Frequency (Hz) Frequency (Hz)

1.E+06 1.E+06

Panel # 12 Before Exposure Panel # 14 Before Exposure

1.E+05 1.E+05
Panel # 12 After Exposure Panel # 14 After Exposure
|Z| (Ohms)

|Z| (Ohms)

1.E+04 1.E+04

1.E+03 1.E+03

1.E+02 1.E+02

1.E+01 1.E+01

1.E+00 1.E+00
0.1 1 10 100 1000 10000 100000 0.1 1 10 100 1000 10000 100000
Frequency (Hz) Frequency (Hz)

Figure 8: EIS results of Panels # 3, 5, 6, 8, 12, & 14 measured in 3.5% NaCl at ambient temperature
before and after exposure to downhole conditions.
 CONCLUSIONS

Following are the main conclusions from this study:

 The performance of six coating systems — applied with the objective of corrosion and scale
prevention on test samples, machined from a downhole carbon steel tubular — tested under
simulated downhole sour gas well conditions, was presented and discussed.

 The six coated panels were prepared by applying a thin layer of high phosphorus electroless
nickel plating (ENP) layer, followed by a second layer, containing added particles like PTFE
(polytetrafluoroethylene), boron nitride, talc, diamond, and silicon carbide.

 The optical photographs of the test panels before and after exposure indicated corrosion attacks,
even though the test was conducted, for screening purposes, under static conditions. Blisters
were also visible to different degrees. Nitrogen gas was used to pressurize the autoclave instead
of methane, which could have been more aggressive.

 The mean contact angles (CA), measured for the six systems, ranged from 71° to 104°. These
values are smaller than the minimum CA for hydrophobic coating surfaces of 110°.

 The initial impedance values, |z|, were of the order of magnitude of 105 ohm, which is lower than
the minimum acceptable threshold value of 108 ohm. These values dropped even further after the
autoclave exposure test.

 Similar initial and final impedance values for the six different coating systems indicate that the
underlayer, which was the same for all, was the main contributor to the overall coating impedance.
The added fillers and the heat treatment did not have a significant effect in this case.

 Based on the above results, the six coating systems presented and discussed in this paper are
not recommended for field application, to coat the internal surfaces of downhole sour gas well
tubulars for corrosion and scale prevention.

ACKNOWLEDGEMENTS

The authors wish to thank Saudi Aramco for permission to publish this work. Also, they wish to thank
Anaam H. Al-ShaikhAli for her assistance in producing the ESEM images; and Waleed A. Al-Obaid for
his assistance in running the contact angle tests; both are of the Research and Development Center of
Saudi Aramco.

REFERENCES

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Corrosion Protection. Paper No. NACE-2015-5673 presented at CORROSION 2015, 15-19 March,
Dallas, Texas, USA. NACE International.

2. Y.T. Al-Janabi, A.M. Al-Ramis, H.M. Al-Mutairi, A.H. Al-Rasheed, and A.A. Jabran, “Life Prediction of
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No. 00759. (Houston/Texas, NACE 2000).
3. Hofmans, J., Nelissen, J., Tixhon, J.-M., & McKeen, L. W. (2012). Engineered Internal Downhole
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