Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors
Abstract
:1. Introduction
2. Types of Corrosion
- Uniform Corrosion: This is the most common type of corrosion and occurs evenly over a large surface area of a material. It is caused by exposure to a corrosive environment, such as water, air, or chemicals.
- Pitting Corrosion: This type of corrosion is characterized by the formation of small holes or pits on the surface of a material. It is caused by localized corrosion, often due to the presence of impurities in the material or environmental factors, such as high chloride levels.
- Galvanic Corrosion: This type of corrosion occurs when two dissimilar metals are in contact with each other and an electrolyte, such as saltwater, is present. One metal becomes anodic and corrodes, while the other becomes cathodic and is protected from corrosion.
- Crevice Corrosion: This type of corrosion occurs in confined areas, such as crevices or seams, where the flow of air and liquids is restricted. This leads to a buildup of corrosive substances and the material corrodes from the inside out.
- Intergranular Corrosion: This type of corrosion occurs along the grain boundaries of a material, causing a loss of material and weakening of the structure. It is often caused by the presence of impurities, such as sulfur or chlorine, in the material.
- Erosion Corrosion: This type of corrosion occurs when a material is exposed to a corrosive fluid that is flowing at a high velocity, causing the material to erode away. This type of corrosion is common in pipelines, valves, and pumps.
- Stress Corrosion Cracking: This type of corrosion occurs when a material is under stress and exposed to a corrosive environment. It is often caused by high tensile stress, high chloride levels, or high temperatures.
3. Classifications of Organic Corrosion Inhibitors
- Inorganic corrosion inhibitors: These inhibitors contain metallic compounds such as nitrates, phosphates, chromates, and molybdates. They work by forming a protective film on the metal surface, which prevents the formation of corrosion cells.
- Organic corrosion inhibitors: These inhibitors contain organic compounds such as amino acids, alcohols, and amines. They work by adsorbing onto the metal surface and forming a barrier between the metal and the corrosive environment. Organic inhibitors are commonly used in industries such as oil and gas, petrochemical, and marine applications.
- Nitrite inhibitors: These inhibitors contain nitrite ions as the active ingredient and are commonly used in cooling water systems and boilers.
- Phosphonic acid inhibitors: This type of inhibitor contains phosphonic acid or its derivatives and is effective at preventing corrosion in high-temperature and high-pressure systems.
- Carboxylic acid inhibitors: Carboxylic acid inhibitors are commonly used in industrial applications and contain compounds such as benzoic acid, salicylic acid, and acetic acid.
- Sulfonic acid inhibitors: Sulfonic acid inhibitors contain sulfonic acid and its derivatives and are used in a wide range of industrial applications.
- Thiophosphoric acid inhibitors: Thiophosphoric acid inhibitors contain thiophosphoric acid and its derivatives and are effective at preventing corrosion in high-temperature systems.
- Ethylenediamine inhibitors: This type of inhibitor contains ethylenediamine as the active ingredient and is used in a variety of industrial applications.
- Amines inhibitors: Amines inhibitors contain amine compounds as the active ingredient and are commonly used in water treatment and oilfield applications.
- Phenol inhibitors: Phenol inhibitors contain phenol or its derivatives as the active ingredient and are used in a variety of industrial applications.
4. Active Functional Groups in Organic Corrosion Inhibitors
- Nitrogen-containing functional groups: These functional groups contain nitrogen atoms, which can form chelating agents with metal ions. The most common nitrogen-containing functional groups used in corrosion inhibitors include amines, imides, and guanidines.
- Oxygen-containing functional groups: These functional groups contain oxygen atoms, which can form a protective film on the metal surface, inhibiting further corrosion. Some of the most common oxygen-containing functional groups used in corrosion inhibitors include carboxylic acids, esters, and ethers.
- Sulfur-containing functional groups: Sulfur-containing functional groups can form a protective film on the metal surface, preventing further corrosion. Some of the most commonly used sulfur-containing functional groups in corrosion inhibitors include sulfonic acids and thiols.
- Phosphorus-containing functional groups: Phosphorus-containing functional groups can form a protective film on the metal surface, inhibiting further corrosion. Some of the most commonly used phosphorus-containing functional groups in corrosion inhibitors include phosphonic acids and phosphates.
- Halogen-containing functional groups: Halogen-containing functional groups, such as halogens (chlorine, fluorine, and bromine), can form a protective film on the metal surface, inhibiting further corrosion.
5. Estimating Organic Corrosion Inhibitors Efficiency
5.1. Electrochemical Techniques
5.1.1. Potentiodynamic Polarization
5.1.2. Electrochemical Impedance Spectroscopy (EIS)
5.2. Weight Loss Tests
- Preparation of specimens: The metal specimens are prepared and cleaned thoroughly. Then, they are coated with a thin layer of the organic inhibitor under study.
- Weight loss measurements: The weight loss of the metal specimens is measured after exposing them to a corrosive environment for a specified period of time. The weight loss is calculated using the following equation:
- Corrosion current density (): The corrosion current density () is calculated using the following equation:
- Corrosion potential (): The corrosion potential () is estimated using a corrosion potential meter. The potential is recorded as a function of time and the steady-state corrosion potential () is determined.
- Comparison with control specimens: Control specimens without the organic inhibitor are prepared and the weight loss and electrochemical estimations such as corrosion potential and polarization resistance are obtained to evaluate the corrosion behavior of the metal [31]. The results obtained from the control specimens are compared with the results obtained from the specimens with the organic inhibitor. The presence of an organic inhibitor in the corrosive environment leads to a decrease in the corrosion current density and an increase in the corrosion potential compared to the control specimens. The efficacy of the organic inhibitor can be determined by comparing the results obtained with the inhibitor with the control specimens. This WLT technique is an effective method to estimate the corrosion current and potential of a metal in the presence of an organic inhibitor. The results obtained from this test provide valuable information on the corrosion protection properties of the organic inhibitor.
5.3. Optical Microscopy
- d(t) is the remaining thickness of the metal after time t;
- is the initial thickness of the metal;
- is the corrosion current density (in A/cm2);
- t is the exposure time (in hours);
- M is the atomic weight of the metal;
- n is the number of electrons transferred in the corrosion reaction;
- F is the Faraday constant (96,485 C/mol);
- A is the surface area of the metal (in cm2).
5.4. XPS
5.5. Scanning Electron Microscopy (SEM)
- Preparation of the sample: The metal sample is prepared for SEM by first cleaning it and removing any surface contaminants. This is typically performed using a solvent cleaning process or an etching process.
- Deposition of the organic inhibitor: The organic inhibitor is then deposited onto the metal surface. This can be performed using various methods, such as chemical deposition, electrodeposition, or physical adsorption.
- SEM imaging: The sample is then placed in the SEM and imaging is performed. The SEM uses a high-energy electron beam to scan the sample and produce a high-resolution image. This image can be used to determine the distribution of the organic inhibitor on the metal surface.
- Current-potential estimation: Current-potential estimations are performed by applying a potential difference between the metal sample and a reference electrode. This creates an electric field, which causes the metal ions to migrate towards the reference electrode. The rate of ion migration is proportional to the corrosion current, which is calculated from equations rather than directly measured.
- Analysis of the data: The corrosion current density and potential are then calculated from the current-potential estimation using appropriate equations. The corrosion potential, Ecorr, can be determined from the Nernst equation:
- 6.
- Interpretation of results: The corrosion current and potential can be used to evaluate the efficacy of the organic inhibitor. A lower corrosion current and a more positive corrosion potential indicate that the organic inhibitor is effectively reducing corrosion.
6. Previous Studies on Using Natural and Synthetic Organic Inhibitors
- Natural organic inhibitors:
- a.
- Using chitosan as a natural inhibitor in the inhibition of the corrosion of mild steel in seawater [52].
- b.
- The use of cinnamon extract as an inhibitor for the corrosion of aluminum in acidic media [53].
- c.
- The application of tannic acid as a natural inhibitor for the corrosion of carbon steel in an aqueous solution [54].
- 2.
- Synthetic organic inhibitors:
- a.
- The effectiveness of benzotriazole as a corrosion inhibitor for aluminum alloys in acidic media [59].
- b.
- The use of triazole derivatives as corrosion inhibitors for mild steel in acidic environments [60].
- c.
- The inhibition performance of imidazoline derivatives in the corrosion of copper in aerated seawater [61].
7. Adsorption Isotherms of Organic Corrosion Inhibitors
8. Mechanisms of Organic Corrosion Inhibitors
- Adsorption: Adsorption is the most frequently observed mechanism of organic corrosion inhibitors. These inhibitors attach themselves to the surface of the metal, creating a protective layer that serves as a barrier between the metal and the corrosive environment. Several factors, including the concentration of the inhibitor, the surface area, and the presence of other species in the solution, can affect this process [79,80].
- Film formation: Organic corrosion inhibitors can also form a film on the metal surface, which protects it from corrosion. This film acts as a barrier, preventing the corrosive agents from reaching the metal surface.
- Electrostatic repulsion: Organic corrosion inhibitors can use electrostatic repulsion to prevent corrosion. These inhibitors can be charged, which allows them to repel corrosive agents. For example, inhibitors with a positive charge can repel negatively charged corrosive ions, while inhibitors with a negative charge can repel positively charged ions [81,82].
- Complex formation: Organic corrosion inhibitors can form complex compounds with the corrosive agents, thereby reducing their effectiveness. This results in a reduction in the corrosion rate as the corrosive agents are neutralized.
- pH adjustment: Organic corrosion inhibitors can also adjust the pH of the solution to a neutral or slightly alkaline level. This helps to reduce the concentration of corrosive agents in the solution, which in turn reduces the rate of corrosion.
- Cathodic protection: Organic corrosion inhibitors can act as cathodic inhibitors by reducing the cathodic reaction rate, thus reducing the rate of corrosion.
- Oxygen scavenging: Organic corrosion inhibitors are compounds that can reduce the rate of corrosion by scavenging oxygen from the solution. By removing oxygen, the formation of corrosive agents that would otherwise cause corrosion is prevented. These inhibitors function by creating a protective barrier on the metal surface, which prevents the corrosive agents from coming into contact with the metal [83,84].
9. Computational Methods
- Molecular dynamics (MDs) simulations: MD simulations can provide insights into the interaction between inhibitors and metal surfaces at the atomic scale. These simulations can be used to study the adsorption behavior of inhibitors, the effect of the molecular structure on inhibitor performance, and the effect of environmental factors such as pH and temperature on inhibitor efficacy [86].
- Density functional theory (DFT): DFT calculations can be used to study the electronic properties of inhibitors and their interaction with metal surfaces. This approach can be used to predict the adsorption energy of inhibitors and to identify the most effective inhibitors for a particular metal surface [76].
- Monte Carlo simulations: Monte Carlo simulations can be used to predict the coverage and distribution of inhibitors on metal surfaces. This approach can provide insights into the mechanism of inhibitor action and can be used to optimize inhibitor concentrations and application methods [87].
10. Comparison Studies
11. Future Outlooks
- Green corrosion inhibitors: With increasing concern about the environmental impact of chemical inhibitors, there is a growing interest in the development of green corrosion inhibitors. These inhibitors are derived from renewable resources, are biodegradable, and are less toxic to the environment. Researchers are exploring natural sources such as plant extracts, essential oils, and biopolymers as potential green inhibitors.
- Nanotechnology: Nanotechnology has shown promising results in the development of corrosion inhibitors due to its ability to enhance the protective properties of coatings and films. Researchers are exploring the use of nanoparticles as corrosion inhibitors or as carriers of inhibitors to enhance their efficiency.
- Computational studies: Computational studies have become an essential tool in the design and development of new inhibitors. With advances in computing power and molecular simulation techniques, researchers can better understand the interactions between inhibitors and metal surfaces and optimize inhibitor structures for maximum effectiveness.
- Synergistic effects: Combining different inhibitors to create synergistic effects is a promising area of research. Researchers are exploring the use of natural and synthetic inhibitors together, as well as the combination of inhibitors with other corrosion protection strategies such as coatings and cathodic protection.
- Application-specific inhibitors: Different industries and applications have specific requirements for corrosion inhibitors. In the future, more research is expected to focus on developing inhibitors tailored to specific industries, such as oil and gas, automotive, or aerospace, to optimize performance and cost-effectiveness.
12. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Source | Natural Inhibitors | Mechanisms of Inhibition | Applications | Advantages | Disadvantages | Ref. |
---|---|---|---|---|---|---|
Plants | Tannins, flavonoids, alkaloids | Formation of a protective layer on the metal surface, adsorption of the inhibitor molecules on the metal surface | Inhibiting corrosion of metals in aqueous solutions | Renewable, biodegradable, low toxicity | Limited effectiveness, degradation over time, sensitivity to environmental conditions | [127,128,129] |
Fungi | Lignin, chitosan, polysaccharides | Formation of a barrier film, adsorption of the inhibitor molecules on the metal surface | Protection of metals against corrosion in aqueous solutions | Low cost, biodegradable, high efficiency | Limited stability, sensitivity to environmental conditions | [130,131,132] |
Microorganisms | Bacteria, yeasts, actinomycetes | Formation of a protective layer on the metal surface, production of organic acids, adsorption of the inhibitor molecules on the metal surface | Inhibiting corrosion of metals in aqueous solutions | Renewable, biodegradable, effective at low concentrations | Limited stability, sensitivity to environmental conditions | [133] |
Natural oils | Castor oil, soybean oil, coconut oil | Formation of a barrier film, adsorption of the inhibitor molecules on the metal surface | Protection of metals against corrosion in aqueous solutions | Low cost, readily available, biodegradable | Limited effectiveness, sensitivity to environmental conditions | [134] |
Polysaccharides | Xanthan gum, carrageenan, starch | Formation of a barrier film, adsorption of the inhibitor molecules on the metal surface | Protection of metals against corrosion in aqueous solutions | Biodegradable, renewable, cost-effective | Limited stability, sensitivity to environmental conditions | [135] |
Plant extracts | - | Adsorption | Metal protection | Abundant, eco-friendly, low cost | Performance may vary depending on the plant species and extraction method | [136,137,138] |
Essential oils | - | Film formation, adsorption, complexation | Oil and gas industries, metal surface protection | Good antimicrobial and antifungal properties, biodegradable | Strong odors may limit their use | [139,140] |
Amino acids | - | Adsorption, complexation | Metal surface protection | Non-toxic, biodegradable, low cost | Limited effectiveness at high temperatures and low pH | [141] |
Polysaccharides | - | Adsorption, film formation | Metal surface protection, concrete reinforcement | Eco-friendly, non-toxic, and biodegradable | Can be time-consuming to prepare and to apply | [142] |
Proteins | - | Adsorption, complexation | Metal surface protection | Biodegradable, non-toxic | Can be expensive and may cause fouling in certain systems | [143] |
Enzymes | - | Adsorption, complexation | Metal surface protection | High selectivity, biodegradable | Limited effectiveness at high temperatures and low pH, can be expensive | [144] |
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Al-Amiery, A.A.; Isahak, W.N.R.W.; Al-Azzawi, W.K. Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors. Lubricants 2023, 11, 174. https://doi.org/10.3390/lubricants11040174
Al-Amiery AA, Isahak WNRW, Al-Azzawi WK. Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors. Lubricants. 2023; 11(4):174. https://doi.org/10.3390/lubricants11040174
Chicago/Turabian StyleAl-Amiery, Ahmed A., Wan Nor Roslam Wan Isahak, and Waleed Khalid Al-Azzawi. 2023. "Corrosion Inhibitors: Natural and Synthetic Organic Inhibitors" Lubricants 11, no. 4: 174. https://doi.org/10.3390/lubricants11040174