Influence of Protection

Abstract
This research work focuses on the synthesis, characterization and processing of potassium silicate/zinc/graphene composites to improve the corrosion performance of zinc-rich coatings. A stable high-modulus potassium silicate composite material was prepared with silica sol and potassium silicate and then, different percentages of graphene were added and ultrasonication process was used to prepare potassium silicate/zinc/graphene composites. Coatings were applied on carbon steel panels with composition of zinc and 0.5 wt.%, 1 wt.%, 1.5 wt.%, and 2 wt.% graphene. SEM was utilized to analyze the structural characteristics of the samples. The coating can be divided into two pieces: the upper layer with high modulus potassium silicate as binder and graphene as filler; the lower layer with high modulus potassium silicate, graphene and zinc particles. The anticorrosive properties of the nanocomposites were investigated by DC polarization technique and electrochemical impedance spectroscopy (EIS). The results of electrochemical tests showed that there exist three stages: the activated stage, the cathodic protection stage and the barrier protection stage. The addition of graphene improves the corrosion resistance of coatings and the best corrosion performance obtained for the nanocomposite sample with 2 wt.% graphene. 
Key words: coating, potassium silicate, waterborne, graphene


1 Introduction
Shop primer, which is also called maintenance primer and known as metal pretreatment primer, is utilized just for the temporary protection of steel surface treatment. It prevents steel from cutting, welding, rust or corrosion. So far, using zinc-rich coatings is a very efficient method for protecting steel structures against corrosion in some aspects of the steel industry[1, 2]. In fact, shop primer has been widely applied as pretreatment primer to many large steel components since the 1960s, such as super tankers, offshore oil and gas drilling platform. At the beginning of immersion, zinc particles provide a cathodic protection of the steel substrate, causing electrical conductivity of dry film by binding to the surface of the base metal and protects the substrate with sacrificial galvanic protection[3]. Then, the corrosion products of zinc powder will gradually deposit to form a layer of protective film on the steel, which may seal the pores in the primer and improve barrier properties[4-7].
Many works are being done to improve the properties of zinc-rich coatings. At present, the effect of waterborne zinc rich coating has almost been comparable with the performance of solvent coating[2, 8]. Inorganic zinc-rich coatings has many features, including low VOC, fast drying, good rust resistance, weld ability, high mechanical performances[9] low maintenance cost and safety[10-13]. In common zinc-rich paint, zinc is usually introduced as spherical pigments with a mean diameter ranging from 5 to 10 μm. The more is the amount of zinc in dry film, the more similar are the film properties to hot dip galvanized coatings[14]. To ensure good electrical contacts between zinc pigments and the cathodic protection of the carbon steel substrate, a high pigment concentration with 92 wt.% to 95 wt.% zinc is required in dry film [14]. However, the high amount of zinc in coating weaken the adhesion properties of the film and Zinc Oxide dust produced in welding is harmful to the health of workers. Therefore, the problem is that high percentage of zinc pigments is needed to increase coating efficiency. On the other hand, the pigment particle size is very effective on the required percentage of zinc pigment[15]. 
So, in this paper the nanoparticles were used to reduce the amount of required zinc. Jagtap et al. found that a specific amount of zinc oxide in zinc-rich coatings could improve the corrosion resistance of zinc-rich coating due to the barrier properties[16, 17]. Y. Cubides[18] found that carbon nanotube can improve the corrosion protection and N. Arianpouya[15] found that PU/Zn/OMMT nanocomposite coatings exhibit superior corrosion protection effect attributed to the nature of clay which have lower water permeability than zinc by itself and extensively help to fill the voids, crevices and pinholes of the polymer and enhance coating adhesion to the substrate and obviously increase the barrier properties of the coating. So, it seems that addition of lamellar pigments to the coating has double protection effect on the efficiency of zinc-rich coating. It is also important to point out the need of decrease of zinc in coatings, which help to save materials and energy[15].
Graphene has gained relevance in many applications[19], e.g. in applications requiring good mechanical and thermal stability [20, 21], low chemical reactivity[22], gas impermeability[23], and good barrier property [23-25]. Because of these properties graphene is gaining scientist’s attention for preparing protective coatings. Several groups have demonstrated the effectiveness of graphene as oxidation resistive[26, 27] and corrosion inhibitive coatings[28, 29]. 
In our work, we showed that the composite coating has much better corrosion protection properties than only zinc-rich coatings. 


2 Experimental
2.1 Preparation of samples
Aqueous solution of potassium silicate (30wt%, the modulus is 3.7) was provided by Xingtai Ocean Chemical Company. In order to increase the modulus, a 30wt% colloidal solution of nano-silica AJN-830 with a particle size of 5-10nm were purchased from Dali Zhongfa Company. And then, the potassium silicate and colloidal solution of nano-silica are mixed until SiO2/K2O molar ratio is 5:1. Zinc dust (1#) with an average particle size of 5-10 μm was offered by Changsha Resucerial New Material Company. Graphene nanoplatelets were purchased from the Suzhou Geruifeng Nanotechnology limited company (China). Paints were made up of the modified potassium silicate and zinc dust. 
Table 1 shows the characteristics of zinc-rich coating. (The solid matter of the binder is about 25%.)
Table 1 Characteristics of coatings
Sample Zinc dust/g Graphene/g Binder/g Graphene/zinc
G1 30 0 30 0
G2 30 0.15 30 0.5
G3 30 0.3 30 1
G4 30 0.45 30 1.5
G5 30 0.6 30 2


2.2 Electrochemical measurements
Electrochemical measurements were conducted in CHI760E electrochemical workstation. A three-electrode system: the coated sample as the working electrodes, a saturated calomel electrode (SCE) as the reference electrode, and the Pt electrode with a diameter of 2 cm as the counter electrode was used for the measurements of open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), and DC polarization technique. A 10-mV perturbation signal was applied to the electrochemical cell to measure electrochemical impedance. All electrochemical measurements were performed in the 3.5 wt% NaCl electrolyte on carbon steel panels coated with different coatings at different exposure times. In this experiment, the corrosion potential (E_corr) and the corrosion current (I_corr) were obtained from the Tafel plots. The Tafel plot facilitated a direct measure of corrosion current to calculate the corrosion rate.


3 Results and discussion
3.1 Morphology and structure of the coatings
Fig 1 shows the surface and the connection of the carbon steel SEM images for G5. The surface of the sample G5 is very smooth and there’s no spherical zinc particles can be seen on the surface (Fig 1A). However, the other side of the coating shows a rough surface which increase the contact area between the coating and the carbon steel (Fig 1B). This shows that the zinc powder disperses unevenly. The sedimentation rate of the zinc powder which is much higher than that of the graphene. can be estimated by Stockes settlement formula:
ω=(g*d^2*(ρ_d-ρ))/(18*μ)
where ω is sedimentation rate; g is acceleration of gravity; d is the particle size of zinc powder; ρ_d is the density of zinc; ρ is the density of solution and μ is the viscosity of solution. The sedimentation rate of graphene is so slow that settlement of graphene is considered not to occur before the coating solidification. The coating can be divided into two pieces: the upper layer with high modulus potassium silicate as binder and graphene as filler; the lower layer with high modulus potassium silicate, graphene and zinc particles. Fig 2 shows the double layer structure of the coating.
  Fig 1 SEM micrographs of surface of the sample G5
 (A) the front surface (B)the opposite surface


 
Fig 2 Sketch map of coating structure
3.2 Corrosion rate of the coatings
Fig3 A shows the Tafel plots of G1, G2, G3, G4 and G5 when the samples have just been immersed in 3.5% NaCl solution, while the Fig3 B, Fig3 C and Fig3 D show the Tafel plots after 1, 3 and 8 days immersion, respectively. A marked change of Tafel plot has taken place when the addition of graphene reaches 1.5% (Fig3 A). The corrosion potential of the coating shifts negatively, while the corrosion current increases obviously. Especially, the corrosion current of the sample G5 is ten times higher than the sample G1, G2 and G3. This means that only 30phr of zinc powder begin to react under the action of graphene. However, the mixed corrosion potential of the coating is still at -0.3-0V (Vs SCE), revealing there’s no cathodic protection. Tafel plots change a lot after 1-day immersion in NaCl solution (Fig3 B). Compared with the blank sample G1, the addition of graphene greatly decreases the corrosion potential of the coating after a period. The corrosion potential of the sample G4 and G5 are stay at -1.0--1.2V (Vs SCE) while the electrode of Fe oxidation equals -0.76V (Vs SCE), so that the conditions of the sacrificial anode cathodic protection are satisfied. What’s more, there exists a period of activation. Only when the coating has passed through a period of activation, and water penetrates the coating will graphene maximize its value. The corrosion current density, I_corr, values of coatings increase with the amount of graphene. I_corr of the sample G4 is probably 100 times as much as the blank sample G1. This means that the addition of 1.5% graphene improves the conductive network between zinc powders and the cathodic protection performance of the coatings. Fig 3 C shows the Tafel plots after 3 days’ immersion. The open circuit potential of all the samples shift positively after 3 days’ immersion. The open circuit potential of G4 moves to -0.28V while that of G5 moves to -0.69V, both of which exceed the threshold -0.76V[18, 30], so that the coatings provide physical shielding instead of cathodic protection. Fig 3 D shows the Tafel plots after 8 days’ immersion. The open circuit potential of all the samples shift positively after 3 days’ immersion. Except G5, graphene in all the other samples has already lost its electronic function. It is also because the coating no longer provides cathodic protection, the corrosion current drops to the previous level, which is the same as the blank sample.
 
Fig3 Potential dynamic polarization plots of the samples with different coatings measured in 3.5wt% NaCl solution. (A) after 0-day immersion (B) after 1-day immersion (C) after 3-days immersion (D) after 8-days immersion 


Table2 Electrochemical parameters obtained from potential dynamic polarization measurements after 0 days immersion of samples.
Samples Electrochemical corrosion measurements
E_corr
(V/SCE) R_P
(MΩ∙〖cm〗^2) β_a
(V/dec) β_c
(V/dec) I_corr
(μA/〖cm〗^2) Corrosion rate
(mm/year)
1 -0.063 0.077 0.27 0.10 0.43 0.0062
2 -0.059 0.064 0.28 0.14 0.56 0.0080
3 -0.064 0.064 0.32 0.11 0.57 0.0081
4 -0.22 0.014 0.52 0.21 4.68 0.067
5 -0.33 0.0050 0.74 0.22 14.85 0.21
 
Fig 4 Sketch map of the coating in activated stage
As to the polarization curve, graphene changes the cathodic and anodic polarization slope. When the coating is just in the early activated stage (Fig 4), the polarization resistance R_p of coatings declined with the increase of graphene (Table 2), decreasing from 0.077 V/dec to 0.0050 V/dec. This indicates that the more graphene, the shorter the duration of activation period. and zinc powder can more quickly produce the cathodic protection effect. For G1, G2 and G3, there’s little difference on the open circuit potential and the cathodic polarization slope although the slope of anodic polarization increases from 0.27 V/dec (G1) to 0.74 V/dec (G5). The open circuit potential of G5 is -0.33V, which has not yet reached the standard of cathodic protection, however, zinc powder has started to react for the I_corr reaches 14.85 μA/〖cm〗^2. 
In neutral solution, the corrosion potential is the mixed potential of oxygen reduction and zinc oxidation:
cathode O_2+2H_2 O+4e^-→4OH^- E_(c.e)=0.16V (vs SCE)
anode Zn-2e^-→〖Zn〗^(2+) E_(a.e)=-1.1V (vs SCE)


 
Fig 5 corrosion polarization diagrams of alloys of the coating under activated polarization control
Table 2 shows the increase of β_a and I_corr and the decrease of E_corr with the addition of graphene. There’re two theories to explain this phenomenon. One is the increase of anodic reaction current I_a and the other is the decrease of anodic equilibrium potential E_(a.e).according to the corrosion polarization diagrams. No matter which theory fit the reality, it is obvious that graphene changes the anodic reaction of the system and zinc particles participate in the reaction. 


Table3 Electrochemical parameters obtained from potential dynamic polarization measurements after 1 day’s immersion of samples.
Samples Electrochemical corrosion measurements
E_corr
(V/SCE) R_P
(MΩ∙〖cm〗^2) β_a
(V/dec) β_c
(V/dec) I_corr
(μA/〖cm〗^2) Corrosion rate
(mm/year)
1 -0.033 0.072 0.21 0.11 0.46 0.0066
2 -0.094 0.030 0.22 0.21 1.52 0.022
3 -0.64 0.012 0.22 0.17 3.56 0.051
4 -1.08 0.00048 0.44 0.19 118.07 1.70
5 -1.01 0.0056 0.46 0.24 12.17 0.18


Table 3 shows that the open circuit potential of G4 and G5 are lower than the threshold -0.76V (Vs SCE). At this stage, water has penetrated the coating, forming a conductive network in which zinc powder contact with each other and graphene makes more zinc powder possible to join in the conductive network. The effect of cathodic protection and the utilization rate of zinc are improved by graphene. In G2, 0.5% graphene dispersed in the whole system is not enough so that there’s little difference between G2 and G1 in providing barrier protection. 




Table4 Electrochemical parameters obtained from potential dynamic polarization measurements after 8 days’ immersion of samples.
Samples Electrochemical corrosion measurements
E_corr
(V/SCE) R_P
(MΩ∙〖cm〗^2) β_a
(V/dec) β_c
(V/dec) I_corr
(μA/〖cm〗^2) Corrosion rate
(mm/year)
1 -0.063 0.085 0.30 0.12 0.44 0.0064
2 -0.058 0.10 0.26 0.10 0.32 0.0046
3 -0.036 0.14 0.21 0.10 0.21 0.0030
4 -0.018 0.19 0.18 0.10 0.15 0.0021
5 -0.19 0.0089 0.80 0.26 9.60 0.14


Table 4 shows the parameters of polarization curves after 8 days’ immersion. The open circuit potential of all the samples are shifted positively. Along with graphene content increases from 0% to 1.5%, the corrosion currents reduce from 0.44 μA/〖cm〗^2 to 0.15μA/〖cm〗^2, and the polarization resistance of coatings increase from 0.083 MΩ∙〖cm〗^2 to 0.19 MΩ∙〖cm〗^2. This means that in this stage, despite there still exists a lot of zinc powder unreacted, the coatings only provide normal physical shielding and all the zinc lose its function, serving as filler. As shown in Fig.6, there’s no difference between the two curves which means that all the zinc particles of G1 didn’t participate in the reaction. However, the addition of graphene changes the situation. The corrosion products of G5 with 2% graphene after 15-days immersion is simonkolleite (Z_n5 〖(OH)〗_8 〖Cl〗_2∙H_2 O)(Fig 7). It means that zinc particles participate in the reaction with the help of 2% graphene and the utilization of zinc has been greatly improved.
  
Fig 6 XRD parttern of G1 before and after corrosion
 
Fig 7 XRD parttern of G5 before and after corrosion
What’s more, the outer layer of graphene can also play a role in blocking the electrolyte, leading to the decrease of the corrosion rate. In the other side, the corrosion rate decreased from 0.0064 mm/year to 0.0021 mm/year also because of the corrosion products, including the oxidation products of zinc, which accumulate in the coating and fill in the gap and result in a tortuous percolation path of the electrolyte. Even all the five samples have the same content of zinc powder, the higher concentration of graphene, the more zinc powder connect with each other by two-dimension structure of graphene. Therefore, G5 still shows the corrosion rate of 9.60 μA/〖cm〗^2.


3.3 Eis of the coatings
The |Z| Bode plot of G1 gives a straight line which corresponds to a capacity (Fig 8). Impedance magnitude measured at 0.01Hz reaches 105, which means that good barrier protection was provided by the coating system and there’s no charge transfer processes on the carbon steel substrate. This behavior results from the low content of zinc particles, all of which are well wetted by potassium silicate. Water can penetrate straight towards the carbon steel substrate through micropores for the long distance between zinc particles. The phase Bode plots show little difference after different days immersion and only one-time constant can be observed at 1-10Hz in the low frequency region.
  Fig 8 Electrochemical impedance spectra of carbon steel coated with G1 at different immersion times in the NaCl solution a) Nyquist diagram b) Bode diagram
  Fig 9 Electrochemical impedance spectra of carbon steel coated with G5 at different immersion times in the NaCl solution a) Nyquist diagram b) Bode diagram


The |Z| Bode plot of G5 shows only 104 compared with that of G1 and there’s resistive behavior at the initial time, following capacitive behavior which is the same as G1 (Fig 9). The peak of phase Bode plot shifts from 100Hz (after 1 day) to 1Hz (after 15 days). This behavior can be attributed to the presence of graphene, which can fill in micropores in the potassium silicate and improve the electrical conductivity of coatings (Fig 10 conductive network). Zinc particles in G5 can participate in the oxidation reaction with the addition of 2% graphene. 
 
Fig 10 Sketch map of the coating in cathodic protection stage


Water penetrates along with the surface of graphene instead of straight toward substrate, which can win more time for zinc particles to take effect (Fig 10 permeation pathway). In addition, there’s a noticeable change between G1 and G5 in the Nyquist representation. Impedance diagram of G1 shows a straight line with high impedance at 0.01Hz, while that of G5 shows an obvious capacity arc. This means that potassium silicate surrounding zinc particles has been dissolved by water and zinc particles in contact with water form a double layer capacitance. At the same time, curvature radius of capacitive arc increases with immersion time. This is probably because many corrosion products adsorbed on the surface of the sample, filling in the coating pores, blocking the other anions involved in the reaction, and graphene blocking the diffusion of dissolved oxygen (Fig 11).
 
Fig 11 Sketch map of the coating in barrier protection stage


4 Conclusions
In this study, a series of PS/Zn/Graphene coatings were synthesized under various graphene loadings by using mechanical agitation and sonication process. SEM was used to observe the structure of the zinc/graphene coatings. It shows that the coating can be divided into two pieces: the upper layer provides barrier protection and the lower layer provides both cathodic protection and barrier protection. It is found that coating corrosion resistance is improved as the amounts of graphene are increased to 2 wt.%. These results show that graphene improves the utilization ratio of zinc powder and the cathodic protection of the coatings at the beginning of immersion and then acts as filler to fill the voids, crevices and pinholes of the polymer in the coating and increases the corrosion resistance of the coatings. So, it was observed that the corrosion protection of zinc-rich coatings is improved as the graphene loading is increased up to 2 wt.% and the best performance was for 2 wt.% graphene that corresponded with electrochemical test results


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