Corrosion Science 113 (2016) 180–182

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Short communication

Effect of supercritical CO2 on corrosion behavior and mechanism of

fiber reinforced pipe
Guanhui Wang a , Lin Xiao a , Zhaosong Liu b , Zhaoxiang Han a , Jia-Hu Ouyang a ,
Dongxing Zhang a,∗
a
School of Materials Science and Engineering, Harbin Institute of Technology, P.O. Box 1405, NO. 66 West Dazhi Street, Harbin 150001, China
b
R & D Center, China Star Optoelectronics Technology Co., Ltd., NO. 92, Tangming Road, Shenzhen, 518132, China

a r t i c l e i n f o a b s t r a c t

Article history: The effect of supercritical CO2 (sc-CO2 ) on corrosion behavior and mechanism of fiber reinforced pipe
Received 1 June 2016 (FRP) in this work. The pitting corrosion occurs on the surface of matrix due to the dissolution by sc-CO2 .
Received in revised form 16 October 2016 A minute change in the constitution of elements and functional groups are observed as well as atomic
Accepted 21 October 2016
ratio of O to C, which increases from 37.23% to 42.43% after treatment. Furthermore, the stiffness of FRP
Available online 22 October 2016
decreases from 6455 N/m2 to 6421 N/m2 suffering from the corrosion of mixture containing sc-CO2 . The
corrosion mechanism of FRP in sc-CO2 can be confirmed as physical dissolution and hydrolysis reaction.
Keywords:
© 2016 Elsevier Ltd. All rights reserved.
A. Polymer
B. IR spectroscopy
B. SEM
B. XPS
C. Pitting corrosion
C. Acid corrosion

1. Introduction now, almost no report focus on this problem, and the corrosion
mechanism is still not very clear.
The novel idea of gas injection of CO2 is an excellent method to In this paper, the accelerated ageing of FRP in a sc-CO2 envi-
postpone global warming and elevate production [1–3]. Inversely, ronment was carried out on self-designed equipment. The surface
the corrosion of metallic equipment and pipes under CO2 environ- morphology, chemical structure and properties of FRP samples
ment is outstandingly increasing [4,5]. Fiber reinforced pipe (FRP), were then investigated. The behavior and mechanism of corro-
as a potential alternate to traditional materials, is widely used in sion for the samples in a sc-CO2 environment was ascertained and
petroleum and chemical engineering industries, due to its excel- proposed.
lent performance such as corrosion resistance, low weight, high
strength and long life span [6]. The polymer matrix of FRP is not an
2. Experimental investigation
inert material and can also be corroded by acid, alkaline and water
during its service time, leading to the degradation of the matrix,
The FRP used for this study consisted of ten lays of fiber rein-
the damage of the reinforcement and the interface failure between
forced diglycidyl ether of bis-phenol A resin cured by o-phthalic
those phases [7].
anhydride. The corroding medium used was a mixture contain-
Theoretically, the effect imposed by sc-CO2 to FRP is not only
ing CO2 gas (99.9%) and de-ionized water. The accelerated ageing
chemical in nature, but also physical due to the increased solvency
method was adopted to evaluate the effect of sc-CO2 on the cor-
of sc-CO2 , which can dissolve small molecules including fillers,
rosion behavior of the FRP. A specially designed circular sealing
additives, and oligomers in the matrix [8]. Both types of corrosion
system was used to conduct the static pressure experiment to main-
will result in the expanding of defects and damage of interface, lead-
tain the supercritical state of CO2 . After conducting the tightness
ing to a noticeable decrease of the mechanical performance. Until
test, the de-ionized water and CO2 was pumped into the system,
increasing the pressure to 8 MPa at a temperature of 65 ◦ C for a
period of one month.
∗ Corresponding author. The internal surface morphology of samples was observed by
E-mail address: [email protected] (D. Zhang). a scanning electron microscope (SEM, Cambridge Instruments, S-

http://dx.doi.org/10.1016/j.corsci.2016.10.022
0010-938X/© 2016 Elsevier Ltd. All rights reserved.
 G. Wang et al. / Corrosion Science 113 (2016) 180–182 181

Fig. 1. SEM morphologies of FRP inner surfaces under different conditions. a1 ) SEM morphology of FRP at initial state; b1 ) SEM morphology of FRP after treatment. a2 ) Partial
enlarged view from a1 ; b2 ) Partial enlarged view from b1 .

240). The chemical structure and composition of FRP was detected

125
by Fourier Transform Infrared Spectroscopy (FTIR, Thermo Nicolet
Corp., Avatar 360, ±0.3 cm−1 ) and X-ray photoelectron spec-
Treated state
troscopy (XPS, Physical Electronics, PHI 5700, ±0.2 eV). Relative 100

Tranmittance (%)
density, resin content and stiffness of FRP sample before and after Initial state
treatment were all tested during this study. All tests were carried
75
out seven times and the results were averaged in this work. The
pipe stiffness k is given by the following equation:
50
F
k= (1)
Y
25
where F is the load, N/mm; Y is the pipe deflection, mm.

4000 3500 3000 2500 2000 1500 1000

3. Results and discussion -1
Wavenumber (cm )
The inner surface morphologies of FRP before and after treat- Fig. 2. FTIR of initial and treated FRP specimens.
ment are shown in Fig. 1. Various holes are found on the surface
of treated samples compare with initial one. And the aggregation
structure of resin in the hole is visibly different in comparison with Table 1
Surface elements composition of FRP initial and treated state by XPS.
the surrounding area, being loose inside and smooth on the edge
in Fig. 1b2 ). These holes proved that the matrix was eroded by fluid Sample Elementary composition (%) Atomic ratio (%)
containing supercritical CO2 . Furthermore, there are many small C O Si Ca O/C
pores with a diameter of 1 ␮m appear on the surface of untreated
Initial state 68.84 25.63 4.72 0.81 37.23
and treated FRP can be seen in Fig. 1a2 ) and b2 ). These pores, are
Treated state 65.48 27.78 5.81 0.93 42.43
generated during the production process of FRP due to the evapo-
ration of solvent [9], act as a tunnel for the medium to penetrate
into the matrix or as an initiator defect for corrosion leading to the
swelling of epoxy resin [10,11], followed by the resolving of small 2.15% respectively, and the O/C composition ratio of FRP increases
molecules and fillers by sc-CO2 [12], which form large voids in the from 37.23% before treatment to 42.43% after treatment. Compo-
local area. nent peaks corresponding to surface functional groups for the C1S
FTIR and XPS were employed to study the chemical structure and region scans is shown in Fig. 3. No change in relative percentages of
composition on the surface of FRP samples pre and post treatment. functional groups C O (287.9 eV) and C H (285.0 eV) can be seen.
As shown in Fig. 2, the absorption peaks of some functional groups, In contrast, the percentage of C O C (288.3 eV) decreases by 1.08%,
such as OH, C O C and C O, are detected by FTIR at 3525 cm−1 , and that of C OH (286.5 eV) increases by 1.41% after treatment. This
1100 cm−1 and 1740 cm−1 respectively. The benzene ring is also trend is very similar to the result of FTIR. It is indicated that some
observed in 1460 cm−1 , 1510 cm−1 and 1610 cm−1 . The absorption chemical reactions occurred between the epoxy resin molecule and
peaks of OH enhanced and that of C O C weakened in FTIR of the mixture containing sc-CO2 . The C O C O group in molecule
treated specimens contrary to that of initial group, and no peak is easier to react with acid medium and then generate new −OH
totally disappearance and emergence in the FTIP spectrum. group theoretically as the results analyzed in XPS and FTIR [13].
Four elements of carbon, oxygen, silicon and calcium are All the variation in microscopic surface morphology and com-
detected on the surface of FRP pre and post treatment by XPS. The position of specimens on microscopic structure ultimately lead
latter two theoretically originate from glass fiber or filling. The ele- to the macroscopic performance degradation. The relative density
ment contents of C, O, Si and Ca are 68.84%, 25.63%, 4.72% and 0.81%, and the resin content decrease from 1.93 g/cm3 to 1.88 g/cm3 and
respectively, for the initial specimen as summarized in Table 1. The from 28.69% to 27.72% after treatment respectively owing to the
content of C decreases by 3.36% and the content of O increases by resin exfoliation, the changes of aggregation and chemical reaction.
182 G. Wang et al. / Corrosion Science 113 (2016) 180–182

2000 2000

1800 1800

Intensity (cps) 1600 1600

1400 1400

Intensity (cps)
C-H C-H
1200 1200

1000 1000 C-OH

800 C-O-C 800
C=O C=O C-O-C
600 600
C-OH
400 400
296 294 292 290 288 286 284 282 280 278 296 294 292 290 288 286 284 282 280 278
Binding Energy (eV) Binding Energy (eV)
Fig. 3. Relative percentage of functional groups on FRP surface by C1S XPS. a) C1S XPS at initial state; b) C1S XPS after treatment.

Eventually, the stiffness of the sample decreases from 6455 N/m2 References
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