Review of several papers related with green inhibitors from 2004 to 2017.
Soluble extract from Opuntia ficus-indica (Nopal extract) has been proposed in this chapter as a green inhibitor due to its component called mucilage, which has the ability to retain water; for this reason, it has been used as metal corrosion protection in machinery pieces, tools and other metallic components that need to be stored for short periods. In this way, three industrial carbon steels (AISI 1018, 1045 and 4140) have been exposed in sulfuric acid (H2SO4) to evaluate the corrosion behavior with or without Nopal extract (NE). Some electrochemical techniques have been implemented to evaluate the corrosion inhibition efficiency (IE) such as DC linear polarization resistance (LPR) and AC electrochemical impedance spectroscopy (EIS). Results indicated a considerable superficial modification of steel in terms of dielectric constant and ion charge capacity. When the NE was added, the corrosion mechanism changed from localized to general attack, decreasing the corrosion rate in all cases. More susceptibility to fail by corrosion was observed in the 1045 carbon steel in comparison with the other two studied steels; these results were confirmed by the percentage of inhibitor’s efficiency of about 95%.
- green inhibitor
- corrosion protection
- Nopal extract
- industrial carbon steel
- corrosion rate
- electrochemical evaluation
- electrochemical impedance spectroscopy
Study of corrosion inhibitors has taken a new role in recent years, since new regulations restrict the use of several components in conventional corrosion inhibitors like nitrites, benzoates, chrome, lead, arsenic, among others, because they are toxic and dangerous to health and environment. Formulations of alternative compounds with more biocompatibility and low costs have led to the development of the green inhibitors also called eco-friendly inhibitors [1, 2]. Main sources from which these inhibitors are extracted come from plants, fruits, seeds, leaves and flowers whose components such as flavonoids, alkaloids and natural oils (pennyroyal oil, jojoba oil, etc.) are considered the inhibitor’s active agent. Those extracts have been studied in low concentration and exposed to different aggressive media to protect metals (mainly carbon steels), obtaining good results at the superficial protection against corrosion during the first hours of exposure.
Figure 1 shows a general classification of the corrosion inhibitors according to its origin. Organic inhibitors are characterized by their high molecular weight structures and are polar molecules. Most organic inhibitors are adsorbed on the metal surface by displacing water molecules and forming a compact barrier. Inorganic inhibitors are salts of some metals, which have a passivation effect and reaction with the metal. Some synthetic compounds can reduce corrosion damage in carbon steels [3, 4, 5] because their oxygen, nitrogen, and sulfur heteroatoms react on the metal surface, blocking active sites where corrosion occurs.
Green corrosion inhibitors are biodegradable and do not contain heavy metals or toxic compounds. Mechanisms of the green inhibitors indicate that ions/molecules are adsorbed onto metal surface, interfering with the anodic and/or cathodic reactions and decreasing the diffusion rate for reactants to the metal surface. Usually, the electrical resistance of the metal surface is decreasing. Since their innovation, some researchers have proposed many plants as prospects to be green corrosion inhibitors. Table 1 shows a review of several papers about green inhibitors collected from 2004 to 2017, where the carbon steels in acid media (HCl and H2SO4) were the most studied, possibly because the total annual cost of metallic corrosion in a country is associated mainly with the corrosion of carbon steels of different industrial sectors. Most of these works were focused on demonstrating the efficiency of these extracts as well as their behavior with respect to temperature, identifying the absorption mechanism from the extract components [6, 7], however, other factors like cost and amount are not mentioned in detail.
|Zanthoxylum armatum||Mild steel||H3PO4||> 90||2004|||
|Simmondsia chinensis||Carbon steel||HCl||98||2004|||
|Artemisia vulgaris||Carbon steel||HCl||85||2004|||
|Datura metel||Carbon steel||HCl and H2SO4||84~97||2005|||
|Mentha pulegium||Carbon steel||HCl||80||2006|||
|Carica papaya||Mild steel||H2SO4||94||2007|||
|Gongronema latifolium||Aluminum||HCl, NaOH||> 90||2007|||
|Opuntia ficus-indica (Cactus)||Aluminum||HCl||94||2007, 2012||[16, 17]|
|Phyllanthus amarus||Mild steel||HCl and H2SO4||> 90||2008|||
|Black pepper||Carbon steel||HCl and H2SO4||98||2008|||
|Zallouh root||Carbon steel||H2SO4||90||2008|||
|Justicia gendarussa||Mild steel||HCl||93||2009|||
|Clove oil||Nickel, inconel 600, 690||HCl||88~92||2009|||
|Lupinus albus||Carbon steel||HCl and H2SO4||86||2009|||
|Murraya koenigii||Mild steel||HCl||~ 94||2011|||
|Marine Alga Caulerpa racemosa||Mild steel||H2SO4||~85||2012|||
|Spirulina Platensis||Mild steel||HCl and H2SO4||~80||2012|||
|Aloe vera||Zinc, Galvanized iron||HCl, H2SO4||88.5||2014|||
|Tagetes erecta||Mild steel||H2SO4||98.07||2014|||
|Watermelon rind||Mild steel||HCl, H2SO4||~86||2014||[31, 32]|
|Mangifera indica (Mango) and Orange||Mild steel, Carbon steel||H2SO4, HCl||97||2014|||
|Coconut coir||Aluminum, Mild Steel||HCl and H2SO4||80||2012,2014||[35, 36, 37]|
|Musa paradisiaca (banana)||Mild steel, SS304||H2SO4, NaCl||82.7||2011,2014||[38, 39]|
|Ficus hispana||Mild steel||HCl||90||2015|||
|Nicotiana tabacum||Mild steel||H2SO4||94||2015|||
|Litchi chinensis||Mild steel||H2SO4||97.8||2015|||
|Capsicum annuum, Citrus aurantium, Moringa oleifera||Copper||HNO3||60~80||2015|||
|Azadirachta indica||Al, Mild steel, Tin, SS, Carbon steel||HCl, H2SO4, HNO3||> 85||2015|||
|Petroselinum crispum (Parsley), Eruca sativa (Arugula) Anethum graveolens (Dill)||Carbon steel||HCl||92||2015|||
|Morinda citrifolia||AISI 1045, AISI 8620||HCl||> 86||2015,2016||[47, 48]|
|Pomegranate||Carbon steel, Mild steel, α-Brass||HCl||> 90||2015,2013,2017||[49, 50, 51]|
|Gentiana olivieri||Mild steel||HCl||92||2016|||
|Roasted coffee||Carbon steel||HCl||94||2016|||
|Calotropis procera leaves||Mild steel||NaCl||> 90||2016|||
|Ocimum basilicum||Carbon steel, Mild steel||NaCl + Na2S, H2SO4||88.5||2016,2012||[56, 57]|
|Cedrus atlantica||Lead||Na2CO3||~ 70||2017|||
Evaluation of corrosion inhibition efficiency was based on the implementation of electrochemical and gravimetric methods; the electrochemical techniques consist of linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS). With LPR was obtained information about the inhibition reaction with the compound, classifying the inhibitor action as anodic, cathodic or mixed. EIS allowed to detect the resistance changes on the surface and how the active sites are reordered through changes at the interfacial capacitance of metal-electrolyte.
Corrosion inhibition efficiency can be calculated through the coverage degree “θ” on the metal surface by the following equations:
where Rct is the charge transfer resistance, icorr is the corrosion current and Vcorr is the corrosion rate. Expressions (1), (2) and (3) are obtained from electrochemical techniques like LPR and EIS, and Eq. (4) is calculated using the gravimetric method. With any of those equations, the efficiency is obtained with:
In general, a good inhibitor must have an efficiency greater than 90%.
Efficiency of an organic compound as a corrosion inhibitor depends mainly on the anchor capacity by chemical or physical interactions on the metal surface, forming multilayers of adsorbed organic molecules that block the active sites of corrosion and retarding the anodic and/or cathodic reactions. Thermodynamic studies with adsorption isotherms (Temkin, Frumkin, Langmuir, Freundlich, among others) have allowed to estimate the stability of the layer adsorbed on the surface. These depend on the physicochemical properties of the active molecules related to the inhibitor functional groups like aromatic rings and amino acids with –NH2 groups, which are readily protonated in acid media and adsorbed on the metal surface through acid anions (Cl−, ) negatively charged. Electron density from the donor atoms, and the interaction between the orbital π from inhibitory and the orbital d of the iron, play an important role in the adsorption type [60, 61, 62].
Investment in the use of inhibitors for industrial scale to prevent corrosion represents a small percentage (1%) worldwide compared with the costs in the use of paints, surface treatments and materials selection, which represent 80% of the investment. The main sectors investing in inhibitors such as petrochemicals (production, synthesis, and refining), water treatment systems, and chemical and food processes, have reported an efficiency of up to 90% in the mitigation of corrosion, saving billions of dollars. However, despite its effectiveness, many of the commercial synthetic inhibitors that are currently used generate problems of toxicity and contamination to the environment. Environmental Protection Agency (EPA) regulations have determined that inorganic inhibitor compounds such as salts of chromates, phosphates and molybdates, as well as organic inhibitors like phosphates, amides or thiols, are dangerous. Due to this problem, green inhibitors open an opportunity for the replacement of these compounds (Table 1) where the synthesis process of natural extracts is of low cost and can be applied in closed systems as pipelines and packaging of pieces for transport. Nowadays, the limitation in the industrial staggering of these green inhibitors is in their preservation, since it has been shown that after 24 h, the natural extract begins to decompose which would imply the use of large volumes of extract to serve the industry .
1.1. Opuntia ficus plant
One plant that has caused interest about their potential as a green inhibitor is Opuntia ficus-indica (Nopal), which is a traditional vegetable in Mexico with a high soluble fiber content. Nopal is classified as a wild plant that survives in desert regions and does not require much water for cultivation. It is said that it has an important ecological performance, as it stops the degradation of the deforested soil, making the arid land productive because of its capacity to retain water. There are about 1600 species in 122 genera of the cactus family, from which comes the Nopal. It has fruits that are edible and are known with the name of Tunas. The soluble fiber of Nopal known as mucilage, which has the capacity to retain up to 30 times its weight in water. For this particular compound, it has been promoted as a good candidate for the production of an ecological inhibitor for the protection of the steel against corrosion [64, 65]. Chemical analysis of mucilage indicates that it contains a large amount of pectin as well as minerals such as calcium, potassium and sodium whose quantities depend on the age of the cladodes (leaves). The presence of these minerals suggests that this plant may remain stable over long periods in alkaline media.
Mucilage is similar in consistency with Aloe vera (slimy) and has been used for the conservation of building materials. Chandra  and Torres Acosta  studied the effects of dehydrated Nopal and Aloe vera powder in the electrochemical performance of reinforcing steel in chloride contaminated concrete. Preliminary results suggest that adding these powders in small concentrations might be suitable for enhancing corrosion resistance of steel in concrete. Therefore, this investigation deals with the performance of Nopal mucilage as a corrosion inhibitor for industrial steels exposed in H2SO4.
2. Experimental details
2.1. Specimens preparation
Three types of carbon steels were evaluated in this research: AISI 1045, 1018 and 4140. The composition of each metal is shown in Table 2. Rods of each steel were cut mechanically to obtain specimens of 25 mm of diameter and 5 mm of thickness for the electrochemical evaluations. The surface preparation was grinding with SiC paper through numbers 80, 240, 320, 400, 600 and 1500 grits until a mirror finish. Finally, the specimens were washed with distilled water, degreasing with acetone and drying with hot air.
2.2. Preparation of Nopal extract
Nopal extract was obtained through the selection of tender cladodes, a cleaning process and removal of thorns, cut and disinfected with 2 ml of chlorine +1 ml of Cu2SO4, assuring the elimination of microorganism and fungi that degrade the extract. Subsequently, it was crushed in an extractor where the pulp was removed from the juice; this last one was heated for 1 h at 78°C with a volume ratio of 2:1 in distilled water. Finally, the concentrated liquid was filtered through a fine sieve to ensure separation of solid particles larger than 180 μm, obtaining the final product as shown in Figure 2.
2.3. Experimental sequence
Electrochemical characterization was carried out in an acrylic cell for flat probes , assembled with an arrangement of three electrodes. Steels 1018, 1045 and 4140 were placed as working electrode (WE), a grid of platinum was placed as a counter electrode (CE) and a calomelane electrode was used as reference electrode (RE). Solution of H2SO4 (0.6 mol·l−1) was used as the test electrolyte, prepared with analytical grade reagents and deionized water. All experiments were performed under standard conditions of temperature and pressure. Figure 3 shows the experimental sequence where the steels in H2SO4 with and without Nopal extract (NE) were evaluated. The relation of Nopal extract and H2SO4 ratio was 50:50 volume %. Open circuit potential (OCP) was monitored to ensure the system stability during 1 h, followed by the electrochemical impedance spectroscopy (EIS) technique, applying a sweep of frequencies from 100 kHz to 10 mHz with 10 mV amplitude. OCP measurement was run again for 1 h to continue with linear polarization resistance (LPR) with an overpotential range of ±25 mV and a sweep speed of 1 mV·s−1. Cycle OCP-EIS-OCP-LPR was repeated for 24 h until record the final behavior with a polarization curve (CP) applying an overpotential of ±1 V at a scan rate of 1 mV·s−1. Corrosion rates, capacitances and resistances for all steels were calculated.
3. Results and discussion
Corrosion potential results are shown in Figure 4, where only the steels exposed in acid medium reported positive potentials with a tendency to move toward more negative (active) potentials when the inhibitor is present, indicating a change in the surface activity of the metal. Figure 5 shows the behavior of the resistance between the metal in the acid medium and the medium with inhibitor (H2SO4 + NE). A considerable growth of the Nyquist semicircle was observed with the addition of NE for the three steels, being the widest semicircle for the 4140 steel, which reaches a value of charge transfer resistance (Rct) of 1400 ohms at the beginning of the evaluation. As the exposure time increases, the semicircle shows a tendency to decrease slightly as a result of the alteration of the protection film formed by the inhibitor. At the end of the monitoring, the Rct values from the inhibitor films do not approach the Rct values of the blank, conserving some protection capacity with respect to the metal without inhibitor.
Semicircle adjustment was performed for each impedance cycles by taking an equivalent electrical circuit (EEC) as shown in Figure 6. Due to the shape of the Nyquist semicircle, the basic configuration called EEC Randles model was selected, which is formed by a resistance in series (solution resistance, Rs) coupled to a constant phase element (CPE) that is in parallel with another resistance attributed to the metal/electrolyte interface (Rct).
To obtain the capacitance values (Cdl) from the constant phase element (CPE), it was necessary to obtain the maximum frequency of the Nyquist semicircle (ωθ max) as well as the α exponent that was calculated during the CPE adjustment, since CPE = F٠s(a−1) where F and s indicate Faradios and seconds, respectively. Results in Table 3 are shown in μF cm−2. Equation (6) shows the calculation to Cdl:
|Jo (A/cm2)||Ecorr vs. SCE (V)||Rp (Ohm ·cm2)||Rct (Ohm ·cm2)||Cdl (μF·cm2)|
|H2SO4 + NE||7.85E-06||−0.545||1015.013||717.162||155.96|
|H2SO4 + NE||7.71E-06||−0.543||1085.28||815.98||185.14|
|H2SO4 + NE||1.15E-05||−0.505||729.44||514.16||120.41|
Polarization curves of carbon steel samples exposed in H2SO4 with inhibitor are shown in Figure 7(A), where a decrease in current corrosion of the three steels studied is observed.
Anodic slope shows a change near the 400 mV, associated with a change of their activation by the presence of a coating from the inhibitor’s organic molecules, limiting the ionic interchange between the metal and electrolyte.
Figure 7(A) shows the behavior of the polarization in which there is a decrease in the flow of current on the three steels exposed to the inhibitor. Figure 7(B) shows the corrosion behavior for all the steels; these values were obtained by extrapolation of Tafel, where the steels show a lower corrosion rate to 1018, 4140 and 1045, respectively; these values remain stable throughout the 24 h of exposure.
Table 3 shows the values obtained with the electrochemical techniques LPR and EIS; a correspondence was observed between the values of resistance for both techniques; however, the resistance values by the impedance technique are lower because they are depurated due to the contribution of the resistance to the solution that has been separated with the adjustment of the EEC. The current indicates that the 1018 and 4140 steels have low corrosion rate. Capacitance values indicate a decrease with the presence of the inhibitor and are lower for 1045 and 1018 steels; these values tend to decrease due to a difficulty of ionic exchange.
Figure 8 shows the metallography obtained for all steels on a macroscopic scale, where for (a)–(c), the area exposed to H2SO4 shows that the main mechanism for the three metals is a combination between pitting and generalized corrosion, being more notable the pitting attack for the 1018 and 1045 steels before the NE addition.
Figure 8(d)–(f) shows the behavior of the steels after exposed to the acid mixture plus the Nopal extract. Change of the corrosion mechanism was observed with the addition of the NE from a localized attack (pitting) to a generalized attack due to the redistribution of the active sites by the presence of the organic molecules from the inhibitor, having better behavior in the steel 1045 where the corrosion was considerably diminished.
Figure 9 shows the efficiency calculated for the three steels, observing the performance of the Nopal extract during the 24 h of exposure. It was observed that steel 1045 obtains the highest percentage of efficiency, which is associated with the inhibitor coverage, and remains constant from the 10th hour of exposure, while the other two steels (1018 and 4140) do not achieve sufficient efficiency values to guarantee their protection.
Opuntia ficus-indica (Nopal extract) was used as a green inhibitor to evaluate the corrosion behavior in the protection of three industrial steels (AISI 1018, 1045 and 4140), exposed in sulfuric acid (H2SO4) plus the addition of NE in the same proportion (50/50 volume %). Corrosion potential showed a tendency to be more negative when the NE was added, forming a compact barrier on the metal surface that increased the surface resistance, according to the growth of the Nyquist semicircles and with respect to the steel substrates.
Charge transfer resistance (Rct) was reduced as the exposition time increased due to the deterioration of the protective film. A 4140 steel reported less corrosion rate with respect to the 1018 and 1045 steels, respectively. Polarization resistance (Rp) showed the same behavior with the best behavior for the steel 4140 after 24 h.
Change of the corrosion mechanism was observed with the addition of the NE from a localized attack (pitting) to a generalized attack due to the redistribution of the active sites by the presence of the organic molecules from the inhibitor, having better behavior in the steel 1045 where the corrosion was considerably diminished.
The NE addition changed the corrosion mechanism in the steels from a localized attack (pitting) to a generalized attack due to the adsorbed inhibitor molecules on the metal surface, reducing the anodic and/or cathodic reactions and as a consequence the corrosion rate.
Alloyed steel (4140) showed a decrease in the inhibitor efficiency with the exposition time, showing better tendency (above 90%) for the 1045 steel. This is possible because the chemical composition of the steel is interacting with the adsorbed organic molecules, increasing or reducing the actives sites for corrosion. Difference in corrosion rate for the 4140 steel with the others was the combination of the green inhibitor and their alloyed elements (Mo and Cr).
The authors wish to thank our institution (CIDETEQ) and (UAEM) for the facilities and the National Council of Science and Technology (CONACYT) for financial support. We appreciate the participation of the student Luis E. Almazán Corona, who actively participated in the experimental development through the program UAEM-SIyEA (Secretary of Investigation and Advance Studies) 3817/2014/CID.