Corrosion Mitigation with Nature-Inspired Green Inhibitors: A Review of Steel Protection in Acidic Media

E-1 Vinod Kumar Swami Professor Department Of Chemistry IASE University Sardarshahar, Rajasthan, India Sanjay Kumar Assistant Professor Department Of Chemistry, Govt. Girls College Neem Ka Thana, Rajasthan, India P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation Corrosion Mitigation with Nature-Inspired Green Inhibitors: A Review of Steel Protection in Acidic Media Paper Id : 20458 Submission Date : 2025-07-06 Acceptance Date : 2025-07-21 Publication Date : 2025-07-25 This is an open-access research paper/article distributed under the terms of the Creative Commons Attribution 4.0 International, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. DOI:10.5281/zenodo.16761910 For verification of this paper, please visit on http://www.socialresearchfoundation.com/remarking.php#8 Abstract This review highlights recent advancements in the use of green corrosion inhibitors for steel in acidic environments, such as those found in industrial processes like acid pickling and oil well acidizing. Traditional chemical inhibitors, though effective, are increasingly restricted due to their environmental toxicity and health hazards. Green inhibitors—sourced from plants, biopolymers, amino acids, and agricultural waste—have gained attention for being biodegradable, non-toxic, cost-effective, and rich in functional groups (e.g., N, O, S atoms, and π-electrons) that enable strong adsorption onto steel surfaces. This adsorption creates a protective layer, effectively reducing corrosion. Inhibition performance, often between 80–97%, is evaluated through methods such as weight loss analysis, gasometric and thermometric techniques, and electrochemical testing (EIS and Potentiodynamic Polarization). Surface characterization tools (SEM, AFM, DFT) confirm the formation of protective films. Most green inhibitors act as mixed-type inhibitors, impacting both anodic and cathodic reactions, with adsorption behavior typically following Langmuir or Temkin isotherms. The review also identifies ongoing challenges—particularly in achieving consistent performance at elevated temperatures, developing standardized testing protocols, and utilizing computational modeling for inhibitor design. Despite these limitations, green inhibitors represent a sustainable and effective solution for corrosion control in industries like oil and gas, marine, construction, and automotive, supporting broader goals of environmental protection and resource efficiency. Keywords Green Inhibitor; Steel Corrosion; Acidic Environment; Weight Loss Method; Electrochemical Impedance Spectroscopy (EIS); Potentiodynamic Polarization (PP); Scanning Electron Microscopy (SEM); Atomic Force Microscopy (AFM); Density Functional Theory (DFT); Langmuir Adsorption Isotherm; Surface Characterization; Eco-friendly Corrosion Control Introduction Steel is indispensable to modern infrastructure—including bridges, pipelines, power plants, automobiles, and buildings—due to its strength, durability, and cost-efficiency. However, in acidic environments such as hydrochloric acid (HCl) or sulfuric acid (H₂SO₄), commonly encountered in industries like pickling, acidizing in oil and gas, and water treatment, steel undergoes rapid corrosion. This degradation compromises structural integrity, necessitates premature replacements, and imposes significant financial, environmental, and safety burdens. Globally, corrosion leads to losses equivalent to 3–4% of GDP, amounting to nearly USD 6 trillion annually. In the U.S. alone, it results in over USD 276 billion in annual costs, with the Department of Defense allocating more than USD 20 billion to corrosionrelated maintenance. Infrastructure sectors are especially vulnerable, as evidenced by corrosion-induced delays and repairs within the U.S. transportation system. The global corrosion inhibitors market, valued at USD 8.82 million in 2024, is projected to reach USD 13.34 million by 2034, growing at a CAGR of 4.22%, driven by the need for efficient corrosion mitigation across industries. Environmentally, corrosion contributes substantially to carbon emissions: steel production for corrosion-induced replacement accounted for 10.5% of global CO₂ emissions in 2021, with 1.6–3.4% directly linked to corrosion. Without effective intervention, this figure could rise to 4.1–9.1% by 2030, undermining global climate goals. Moreover, approximately 490 million tons of steel are discarded annually due to corrosion, exacerbating resource depletion and emissions. Although it is impossible to eliminate corrosion entirely, various strategies can significantly minimize its occurrence and impact. These strategies typically involve altering the electrochemical potential, applying protective surface coatings, optimizing structural design, selecting appropriate materials, adjusting environmental conditions, and utilizing corrosion inhibitors as an effective line of defense [1-4]. Objective of study This paper highlights the recent advancements in the use of green corrosion inhibitors for steel in acidic environments, such as those found in industrial processes like acid pickling and oil well acidizing. Review of Literature Traditional corrosion inhibitors such as chromates, phosphates, and amines are widely used due to their effectiveness; however, their application raises significant E-2 P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation environmental and health concerns owing to their toxicity and persistence in ecosystems. These compounds can contaminate soil and water, posing long-term risks to both human health and biodiversity. In response to these challenges, green corrosion inhibitors— sourced from renewable materials like plant extracts, amino acids, agro-waste, and biopolymers—have emerged as a promising and sustainable alternative. These natural substances are abundant in active functional groups, such as heteroatoms (e.g., nitrogen, oxygen, sulfur) and π-electrons, which promote strong adsorption onto metal surfaces, especially in acidic environments where corrosion is most aggressive. This adsorption forms a protective barrier that impedes corrosive agents, thereby enhancing the durability and lifespan of metallic structures. In addition to being biodegradable and non-toxic, green inhibitors are cost-effective, widely available, and environmentally benign, making them suitable for applications in various sectors including oil and gas, construction, automotive, and marine industries. Their use aligns with global efforts to minimize chemical footprints, reduce waste, and promote resource efficiency. Moreover, the valorization of agro-industrial byproducts and waste materials in the development of these inhibitors supports circular economy principles, encouraging innovation in green chemistry and sustainable materials science. As research advances, the formulation and performance optimization of green inhibitors continue to improve, paving the way for their broader adoption in industrial corrosion control strategies [5-7]. Main Text 2. Mechanism of Inhibition Green corrosion inhibitors primarily protect metal surfaces through adsorption, where the inhibitor molecules adhere to the steel surface and form a compact, protective layer. This adsorbed film acts as a physical barrier, preventing aggressive species—such as hydrogen ions, oxygen, and chloride ions—from reaching the metal surface. As a result, the electrochemical reactions responsible for corrosion, including both anodic (metal dissolution) and cathodic (hydrogen evolution or oxygen reduction) processes, are significantly suppressed. The adsorption mechanisms involved are typically a combination of physisorption and chemisorption. Physisorption occurs through weak van der Waals forces, while chemisorption involves stronger chemical bonds, often facilitated by the presence of functional groups containing heteroatoms such as nitrogen, oxygen, sulfur, or phosphorus. These atoms donate lone pair electrons or π-electrons to vacant d-orbitals on the metal surface, enhancing the stability and coverage of the protective layer. Moreover, the nature and efficiency of adsorption depend on various factors, including the molecular structure of the inhibitor, its solubility, the pH of the environment, and the presence of other ions. In many cases, different adsorption interactions can act concurrently, enhancing the overall inhibitory effect. This synergistic action makes green inhibitors particularly effective in acidic media, where corrosion rates are typically high [8-12]. Figure: Corrosion inhibition mechanism 3. An Overview of previous study of Green inhibitor towards steel corrosion In recent decades, growing interest in sustainable and eco-friendly approaches to metal protection has made the development of green corrosion inhibitors a prominent area of scientific research. In this regard, numerous studies have explored the use of green, cost-effective, and eco-friendly plant-based extracts as corrosion inhibitors for mild or carbon steel in acidic environments. These natural inhibitors have shown promising efficiency in mitigating corrosion and are typically evaluated using techniques such as weight loss measurements, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, and surface analysis. Shahmirzadi et al. [13] investigated the inhibition efficiency of green walnut husk (GWH) as a corrosion inhibitor for carbon steel in 1 M HCl. Similarly, Mourya et al. [14] evaluated the extract of Tagetes erecta (marigold flower) for its corrosion inhibition performance on mild steel in 0.5 M H₂SO₄ using gravimetric, potentiodynamic polarization, and EIS methods. Wan et al. [15] reported high efficacy of soybean extract (SE) as a green corrosion inhibitor for carbon steel in acidic media. Dehghania et al. [16] employed Chinese gooseberry fruit shells—an inexpensive waste material—for the extraction of corrosion inhibitors to protect mild steel in 1 M HCl. Rajendra et al. [17] examined the inhibition properties of Henna for mild steel in an acidic E-3 P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation medium. Abdel Hameed et al. [18] used Spinacia oleracea (spinach) extract to inhibit carbon steel corrosion in 1 M HCl. Abu-Dalo et al. [19] studied the effectiveness of exudate gum from Acacia trees (gum acacia) on mild steel corrosion in acidic media. Al-Fakih et al. [20] investigated turmeric and ginger rhizome extracts as corrosion inhibitors in 1 M HCl. Ebenso et al. [21] evaluated the ethanol extract of Piper guinensis (EEPG) for mild steel corrosion inhibition. Similarly, Ali et al. [22] assessed the inhibitory effects of Citrus sinensis extract on carbon steel in 0.5 M H₂SO₄. Berrissoul et al. [23] investigated the corrosion inhibition of Artemisia alba (AHA) for mild steel in 1 M HCl. Saxena et al. [24] examined the inhibition effect of Saraca asoca seed extract in 0.5 M H₂SO₄. Chen et al. [25] studied Solanum tuberosum leaf extract (STLs) as a green inhibitor for Q235 steel in acidic medium. The effect of Thymus algeriensis extract (TEA) on mild steel corrosion in 1 M HCl was studied by Hamdani et al. [26], using weight loss, polarization, and EIS techniques. Wanga et al. [27] demonstrated that Ficus tikoua leaf extract is an effective and biodegradable corrosion inhibitor for carbon steel in HCl. Al-Moubarakia et al. [28] conducted experimental and theoretical evaluations of black mustard seed extract as a sustainable green inhibitor for mild steel in H₂SO₄. Haldhar et al. [29] used weight loss, Tafel, and EIS to assess the inhibition effect of Citrus aurantifolia leaves extract in 0.5 M H₂SO₄. Gopiraman et al. [30] investigated Brugmansia suaveolens (BS) and Cassia roxburghii (CR) extracts as corrosion inhibitors for mild steel in 1 M HCl. Oguzie et al. [31] evaluated the calyx extract of Hibiscus sabdariffa for corrosion control in 2 M HCl and 1 M H₂SO₄ using gasometric techniques. Choudhury et al. [32] utilized Paederia foetida leaf extract for inhibiting mild steel corrosion in 1 M HCl. Luffa cylindrica leaf extract (LCLE) was investigated by Ogunleye et al. [33] using gravimetric analysis and surface characterization techniques. Qianga et al. [34] explored the corrosion inhibition of X70 steel using Ginkgo leaf extract (GLE) in 1 M HCl, assessed through electrochemical measurements. Alvarez et al. [35] tested Rollinia occidentalis extract and two isolated acetogenins—Rolliniastatin-1 and Motrilin—for corrosion inhibition in acidic solutions. Abdallah et al. [36] examined the inhibitory actions of natural extracts from curcumin, parsley, and cassia bark for carbon steel corrosion in 0.5 M H₂SO₄. Kaban et al. [37] assessed the corrosion inhibition potential of white tea extract in acidic conditions. Finally, Ogunleyea et al. [38] investigated the efficacy of Mondia whitei root extract (MWE) for protecting mild steel in 0.5 M HCl, using weight loss, surface morphology, and depth of attack evaluations. 4. Corrosion Monitoring Methods This review highlights various corrosion monitoring techniques employed to evaluate the inhibition efficiency of green inhibitors in mitigating steel corrosion in acidic environments. These methods include weight loss measurements, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, surface morphology analysis, and other electrochemical and gravimetric approaches. 4.1 Weight loss measurement: Weight loss measurement is one of the simplest and most widely used methods for evaluating corrosion rates and inhibitor efficiency, particularly in laboratory studies involving metals exposed to corrosive environments. In this method, a pre-weighed metal specimen (such as mild steel or carbon steel) is immersed in a corrosive solution, typically an acidic medium like HCl or H₂SO₄, for a specified duration. After the exposure period, the specimen is cleaned to remove any corrosion products and then reweighed. The difference in weight before and after exposure reflects the amount of metal lost due to corrosion, allowing researchers to calculate the corrosion rate and assess the effectiveness of corrosion inhibitors [16-23]. The percentage corrosion inhibition efficiency was calculated as: η % = 100 (ΔWU - ΔWi)/ ΔWU Where, ΔWU: Weight loss of metal in uninhibited solution, ΔWi: Weight loss of metal in inhibited solution The degree of Surface coverage () of metal specimen by inhibitor was calculated as: = (ΔWU - ΔWi)/ ΔWU The corrosion rates can be calculated by the following equation: Corrosion rate (mm/yr) = (Weight loss x 87.6)/ DAT Where, D: density of metal, A: surface area of metal specimen, T: time exposure E-4 P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation 4.2 Hydrogen Evaluation: The hydrogen evolution method is a classical and effective technique used to evaluate the corrosion rate of metals in acidic environments, particularly in reactions where hydrogen gas is produced as a byproduct of the corrosion process. When metals such as mild steel are exposed to acidic media like HCl or H₂SO₄, corrosion occurs, and hydrogen gas is evolved during the cathodic reaction: This method involves measuring the volume of hydrogen gas released over time, which reflects the corrosion activity. Hydrogen evolution is widely used in studies of green corrosion inhibitors to assess their efficiency. The presence of plant-based inhibitors typically reduces the corrosion rate, which is indicated by a measurable decrease in the volume of hydrogen gas evolved. This makes the hydrogen evolution method a reliable and straightforward tool for the initial screening of natural extracts as eco-friendly corrosion inhibitors [18, 19, 21, 28, 31]. 4.3 Thermometric Method: This method is based on monitoring the temperature change of a corrosive solution during the metal corrosion process. When a metal such as mild steel corrodes in an acidic medium (e.g., HCl or H₂SO₄), the reaction between the metal and acid is exothermic, resulting in a rise in temperature. The rate and magnitude of this temperature increase are directly related to the corrosion activity [21]. The Reaction Number (RN) is calculated as: Where: Tmax = Maximum temperature recorded, TInitial= initial temperature, t= time (in minutes) A lower Reaction Number (RN) in the presence of a green inhibitor indicates reduced corrosion activity and higher inhibition efficiency. In thermometric studies, a smaller temperature rise confirms the effectiveness of plant-based extracts in inhibiting metal corrosion. 4.4. Electrochemical Methods 4.4.1. Electrochemical Impedance Spectroscopy (EIS): Electrochemical Impedance Spectroscopy (EIS) is a powerful and non-destructive technique widely used to evaluate corrosion behavior and inhibitor performance in metal-electrolyte systems. It works by applying a small alternating current (AC) signal over a range of frequencies to the metal surface and measuring the resulting impedance. The response provides valuable information about the electrochemical processes occurring at the interface, such as charge transfer resistance, double-layer capacitance, and diffusion effects. In corrosion studies, EIS helps quantify how effectively an inhibitor impedes the corrosion reaction, often through an increase in charge transfer resistance and changes in capacitive behavior. It is particularly useful for understanding the protective film formation and the mechanism of inhibition, making it a key method for evaluating plant-based or green corrosion inhibitors in acidic environments [22-24, 28]. 4.4.2. Potentiodynamic Polarization: Potentiodynamic polarization is an electrochemical technique commonly used to investigate the corrosion behavior of metals and assess the efficiency of corrosion inhibitors. It involves sweeping the electrode potential at a controlled rate and measuring the resulting current to produce a polarization curve. This curve reveals important parameters such as corrosion potential (Ecorr), corrosion current density (Icorr), and the nature of the inhibitor (anodic, cathodic, or mixed-type). By comparing the corrosion current densities in the presence and absence of an inhibitor, one can determine the inhibitor's efficiency. The method provides insight into how inhibitors influence the anodic metal dissolution and cathodic hydrogen evolution reactions, making it a valuable tool for studying the mechanisms of green inhibitors in acidic environments [18, 20, 25, 27, 34]. 4.5. Methods for Surface Morphology Analysis 4.5.1. Scanning Electron Microscopy (SEM): Scanning Electron Microscopy (SEM) is an advanced surface analysis technique used to examine the morphology and microstructural changes on metal surfaces before and after corrosion. It operates by scanning the surface of a specimen with a focused beam of high-energy electrons, which interact with the atoms in the material to produce signals that contain topographical and compositional information. In corrosion studies, SEM is employed to observe surface damage, such as pitting, cracks, or uniform corrosion, and to evaluate the protective effect of corrosion inhibitors. When green inhibitors are used, SEM images can confirm the formation of a protective layer on the metal surface, indicating effective corrosion prevention. This technique provides visual evidence that complements electrochemical data, making it essential for understanding inhibitor performance at the microscopic level [16, 19, 27, 37]. E-5 P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation 4.5.2. Atomic Force Microscopy (AFM): Atomic Force Microscopy (AFM) is a highresolution surface characterization technique used to analyze the topography and roughness of materials at the nanoscale. It works by scanning a sharp tip attached to a flexible cantilever across the surface of a sample. As the tip moves, it experiences forces from the surface, causing the cantilever to deflect. These deflections are measured using a laser system and translated into a detailed 3D image of the surface. In corrosion studies, AFM is used to assess surface changes caused by corrosive attack and to evaluate the effectiveness of corrosion inhibitors. When green inhibitors are applied, AFM can reveal smoother surfaces and reduced roughness, indicating the formation of a protective layer and decreased corrosion activity. This technique provides precise, quantitative surface data, making it valuable for confirming the protective action of ecofriendly inhibitors [16, 29, 34, 37]. 4.5.3. Energy Dispersive X-ray Spectroscopy (EDX or EDS): Energy Dispersive X-ray Spectroscopy (EDX or EDS) is an analytical technique used alongside Scanning Electron Microscopy (SEM) to determine the elemental composition of materials. It works by directing a focused electron beam onto the sample surface, which causes the emission of characteristic X-rays from the elements present. Each element emits X-rays at specific energies, allowing for qualitative and quantitative analysis of the sample’s composition. In corrosion studies, EDX is used to identify the elements on the metal surface before and after exposure to corrosive environments. When green inhibitors are applied, EDX can confirm the presence of elements associated with the inhibitor film and detect changes in surface chemistry, providing evidence of inhibitor adsorption and protective layer formation. This makes EDX a valuable tool for understanding the interaction between metal surfaces and corrosion inhibitors at the elemental level [23,30,37]. 4.5.4. Density Functional Theory (DFT): Density Functional Theory (DFT) is a quantum mechanical modeling method used to investigate the electronic structure of atoms, molecules, and materials. It is based on the principle that the ground-state properties of a many-electron system can be determined using electron density rather than wave functions, making it computationally efficient. In corrosion inhibition studies, DFT helps predict the reactivity and interaction of inhibitor molecules with metal surfaces by calculating parameters such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), energy gap, and charge distribution. These values provide insights into the adsorption behavior, stability, and inhibition potential of green inhibitors. By simulating how molecules interact with metal atoms at the atomic level, DFT supports the experimental findings and helps in designing more effective ecofriendly corrosion inhibitors [16, 27, 28] 5. Adsorption Isotherm 1. Adsorption isotherms describe the way corrosion inhibitor molecules attach themselves to a metal surface from a solution at a constant temperature. These models help in understanding the interaction between the inhibitor and the metal by relating the concentration of the inhibitor in the solution to the amount adsorbed on the metal surface. Two of the most commonly applied isotherms in the study of green corrosion inhibitors are: 2. Langmuir Isotherm, which assumes that adsorption occurs in a single layer on a uniform surface without interaction between adsorbed molecules, providing a simple linear relationship between surface coverage and inhibitor concentration [16-21,27-35]. 3. Temkin Isotherm, which accounts for interactions among adsorbed molecules and suggests that the heat of adsorption varies with the degree of coverage, reflecting a more complex adsorption behavior [22,26, 36]. Analyzing which adsorption isotherm best fits the experimental data helps determine whether the inhibitor interacts physically or chemically with the metal surface, providing insights into the inhibition mechanism. In this review, green inhibitors are commonly observed to follow the Langmuir and Temkin adsorption isotherms. Result and Discussion This review of gravimetric, thermometric, and electrochemical studies demonstrates that green inhibitors exhibit impressive inhibition efficiencies exceeding 90% at low concentrations against steel corrosion in acidic environments. The inhibition efficiency consistently improves with increasing inhibitor concentration, a trend well-supported by adsorption isotherm analyses. These inhibitors also maintain strong performance at elevated temperatures and higher acid concentrations, making them effective for prolonged use. Potentiodynamic polarization studies reveal that green inhibitors typically act as mixed-type inhibitors, affecting both anodic and cathodic reactions. Furthermore, electrochemical and surface morphology investigations confirm the formation of a protective layer on the metal surface. Adsorption isotherm models, such as Langmuir and Temkin, suggest that the inhibition mechanism involves a combination of physical and chemical adsorption, frequently leading to the formation of monoor multilayer protective films on the steel surface. E-6 P: ISSN No. 2394-0344 RNI No. UPBIL/2016/67980 VOL.- X , ISSUEIV July - 2025 E: ISSN No. 2455-0817 Remarking An Analisation Conclusion Green inhibitors are eco-friendly, cost-effective, readily available, and demonstrate great potential for protecting steel against corrosion in acidic environments. 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