Corrosion Resistant Coatings

Utilizing Hydrophobic Nanoparticles

PRESENTATI O N TO OW ENS CO RNI NG
O RGANIC ANALYTIC AL LAB
7/ 18/ 2018
 Corrosion
• Natural, spontaneous process
• Has a large economic cost
• 276 billion total annual cost1
• Oil and Gas Industry (1.4 billion annually)1

Off-shore Spending2 On-Shore Spending2

3%

22% 26% 33%

Coatings
5%
Monitoring
70%
Chemicals 8%
33%
Cathodic Protection

1. "Corrosion in the oil and gas industry," http://www.nace.org/Corrosion-Central/Industries/Oil---Gas-Production/

2
2. R. Tems, A.M. Al-Zahrani. "Cost of corrosion in oil production and refining," Saudi Aramco Journal of Technology, 2- 14, 2006.
New Corrosion Resistant Coatings

3
Methodology of Creating Hydrophobic
Nanoparticles
• Diazonium salt chemisty

R group
-CH3 (methyl)
-CH2CH3 (ethyl)
-CH2CH2CH2CH3 (butyl)

4
 Characterization of Nanoparticles
% Transmission

• Fourier Transform Infrared

Spectroscopy (left) and Solid
State 13C Nuclear Magnetic
Resonance (right) both confirm
Unmodified the attachment of organic groups
-1
1617 cm
-1
1314 cm Methyl
Ethyl
Butyl

1500 1000 500

250 200 150 100 50 0
-1
Wavenumber (cm ) ppm

5
 Characterization of Nanoparticles
• Water Contact Angle

Nanoparticles Contact Angle (n=3)

Unmodified CeO2 -

Methyl grafted CeO2 33.6° ± 6.7°

Ethyl grafted CeO2 62.5° ± 6.5°

Butyl grafted CeO2 124.9° ± 6.9°

6
Fabrication of Nanocomposite Coatings
•Watts Bath Electrodeposition
• 300 g/L NiSO4
• 45 g/L NiCl2
• 40 g/L Boric Acid
• Operated at 45°C

•CeO2 Nanoparticles 10 g/L

•Stainless Steel (430) substrate

7
 Corrosion Performance of Coatings
• Potentiodynamic Polarization
Ni-CeO2
0.4
Ni-CeO2-methyl

0.2
Ni-CeO2-ethyl
𝛽$ 𝛽!
Ni-CeO2-butyl
𝑖!"## =
2.3(𝛽$ + 𝛽! )𝑅%
Potential (V)

0.0

-0.2
Coating Ecorr (V) Rp (kΩ/cm2) Icorr (µA/cm2)
Ni-CeO2 -0.181 70.6 ± 10.2 0.47±0.05
-0.4
Ni-CeO2-methyl -0.221 127.6 ± 7.8 0.27±0.08

-0.6
Ni-CeO2-ethyl -0.170 212.5 ± 16.9 0.17±0.02
Ni-CeO2-butyl -0.270 21.3 ± 3.4 1.53±0.22
-10 -8 -6 -4 -2 0
log (j)

8
Unique Problem with Corrosion Exposure
• Open Circuit Potential Immersion Test
• Imperfect Mounting of Samples
• Crevice Corrosion
• Invalid Measurements

9
Design of a New Electrochemical Testing
Cell

10
Performance of 3D Printed Cell
-0.05 Ni-CeO2
Ni-CeO2-methyl
-0.10
Ni-CeO2-ethyl

Open Circuit Potential (V)

Ni-CeO2-butyl
-0.15

-0.20

-0.25

-0.30

-0.35

-0.40

0 5 10 15 20 25 30
Day

11
 Synthesis of Diazonium Salts
(A)
•Peak at 2300 cm-1 characteristic of the
N≡N stretching vibration (A) 4-methylphenyl diazonium

•Method of characterization does begin

% Transmission
to fail depending upon stability of the (B) 4-ethylphenyl diazonium (B)
diazonium salt
(C) 4-n-butylphenyl diazonium

-1
(C) ~2300 cm

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

12
 4-n-butyl CeO2 13C NMR

•Lack of 4 separate peaks is simply due (A)

to the lower resolution of solid state-
NMR

(B)

50 40 30 20 10 0 -10
ppm

13
Characterization of Nanoparticles

Derivative of Weight Change (-Dmg/D T)

• Thermogravimetric Analysis
0.10 0.08

Bare CeO2 0.07

4-methylphenyl CeO2
0.08
0.06

• Multilayers possible 0.06

0.05

0.04

• Loading for each grafted 0.04

0.03

nanoparticle is ~8% by weight 0.02

0.02

0.01

0.00 0.00
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800

Temperature (°C) Temperature (°C)

0.08

0.05 4-ethylphenyl CeO2 0.07

4-butylphenyl CeO2
0.04 0.06

0.05
0.03
0.04

0.02 0.03

0.02
0.01
0.01

0.00 0.00
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700

Temperature (°C) Temperature (°C)

14
XRD Analysis

111
Bare CeO2
4-methyl grafted
4-ethyl grafted
4-n-butyl grafted

220
200

311
222

400
Absolute Intensity

20 30 40 50 60 70

2q (°) 15
 XRD
Intensity (cps)

Ni-CeO2-4-butyl
Ni-CeO2-4-ethyl Sample Particle Size (nm) (n=5)
Ni-CeO2-4-methyl Ni-CeO2 35 ± 2
Ni-CeO2
Ni-CeO2-4-methyl 31 ± 1
Ni-CeO2-4-ethyl 23 ± 3
(11 1) (2 00 ) (SS) (2 20 ) (SS ) (3 11 )
Ni-CeO2-4-butyl 32 ± 2
30 40 50 60 70 80 90 100
2-theta
16
SEM

17
EDS
Counts

Energy (keV) 18
ICP-MS Analysis of Cerium Oxide Content

Coating Amount of Ni (mg) Amount of CeO2 (ug)

Ni-CeO2 9.2 ± 0.5 16 ± 3

Ni-CeO2-4-methyl 9.5 ± 1.1 11 ± 2

Ni-CeO2-4-ethyl 9.4 ± 1.7 8±1

Ni-CeO2-4-butyl 9.0 ± 1.6 5±2

19
 EIS
-400000 1000000
Ni-CeO 2-butyl
Ni-CeO2-ethyl
-350000 Ni-CeO 2-ethyl
Ni-CeO 2-methyl 100000 Ni-CeO2-butyl
-300000 Ni-CeO 2 Ni-CeO2-methyl
10000 Ni-CeO2
-250000
Eq. Circuit Fit
Zim

Zmag
-200000 1000

-150000
100
-100000

10
-50000

0 1
0 50000 100000 150000 200000 250000 300000 0.001 0.01 0.1 1 10 100 1000 10000 100000
Zreal Frequency
20
 Nanoindentation
8
220

200

Young's Modulus (GPa)

7
Hardness (GPa)

180

6
160

140
5

120

4 100
0 1 2 3 4 0 1 2 3 4

# of Carbons # of Carbons

21