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Eucalyptine base polyaniline, as an intrinsic polyaniline, has a molecular backbone composed of unique quinone-benzenediamine alternating units, presenting a metallic luster ranging from emerald green to deep blue. The most remarkable characteristic of this form lies in its protonic acid doping molecular switch effect: when exposed to protonic acid, the quinone rings in the molecular chain undergo reversible protonation, and the rearrangement of the electron cloud leads to the transformation of the quinone structure into the benzene structure, instantly forming polarized energy levels within the band gap, and the electrical conductivity can jump from an insulating state of 10^-10 S/cm to a semiconductor state of 1-10 S/cm. This unique doping mechanism does not involve changes in the number of main chain electrons, but can achieve an insulator-conductor transition simply by switching the acid-base environment, making it an ideal material for chemical sensors. The imine nitrogen atoms on the molecular chain can not only combine with protons but also coordinate with metal ions, endowing it with the ability to capture heavy metal ions. In the field of corrosion prevention, its redox potential is precisely within the metal passivation range, and it can induce the formation of a dense oxide layer on the alloy surface through charge transfer. This material also has excellent environmental stability and solution-processability. Through functionalized acid doping, its hydrophilicity and band structure can be further regulated, demonstrating great potential in flexible electronics, electromagnetic shielding, and intelligent coatings.
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Chemical Formula |
Li2O |
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Exact Mass |
30 |
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Molecular Weight |
30 |
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m/z |
30 (100.0%), 29 (16.4%) |
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Elemental Analysis |
Li, 46.45; O, 53.55 |
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Emeraldine base polyaniline is a polymer compound with special electrical and optical properties, which can exhibit conductivity and electrochemical properties after doping. It has a wide range of applications, including conductive materials, sensors, electronic devices, optical devices, and solar cells.
paint
Polyaniline coating, also known as coating, is a mechanical coating method used to form a uniform and complete polyaniline anti-corrosion film on the surface of metals such as cold-rolled steel, low-carbon steel, aluminum, copper, etc. Its anti-corrosion mechanism is to passivate the metal, form a protective oxide layer on the metal surface, and apply a suitable coating to cause the migration of corrosion potential, thereby reducing the corrosion rate of the metal. Moreover, due to its many advantages such as easy availability of raw materials, simple synthesis, no pollution, and light weight, it is considered a new generation of environmentally acceptable high-efficiency anti-corrosion coatings.
However, PAn is difficult to process and is insoluble in conventional organic solvents. Pure polyaniline has poor adhesion to metals, is expensive, and has low utilization, which poses certain obstacles in practical application. People usually use polyaniline as an additive in anti-corrosion coatings to form polyaniline based anti-corrosion coatings. Polyaniline coatings can be classified into three types based on their substances: single polyaniline coatings, coatings with polyaniline as primer, and blended coatings of polyaniline and traditional coatings.
In 1985, Deberry discovered that the polyaniline film electrodeposited on stainless steel could significantly reduce the corrosion rate of stainless steel in sulfuric acid solution. In fact, it was a single polyaniline coating, where aniline was directly deposited on the metal electrode surface through electrochemical polymerization reaction in acid solution to obtain a polyaniline coating. But this method is difficult to apply to larger metal components.
Polyaniline primer coating refers to the application of traditional polymers as topcoats on top of polyaniline coatings, forming a composite coating with polyaniline.
Its advantage is that there is no need to consider the dispersibility of polyaniline in the coating, and each coating plays its own role. The anti-corrosion performance is the sum of these effects, and the topcoat layer generally provides physical shielding. The joint research team of Los Alamos and NASA in the United States has discovered for the first time that polyaniline can be used as a corrosion-resistant coating for medium carbon steel.
Polyaniline and traditional coating blend coating refers to the process of mixing polyaniline powder with conventional coating film-forming substances (such as epoxy resin, alkyd resin, etc.) and applying them to obtain polyaniline blend anti-corrosion coating. This method is the most commonly used method for studying the anti-corrosion performance and mechanism of polyaniline. It is different from coatings with polyaniline as the primer, and the anti-corrosion performance of the coating is the result of the organic interactions of each component. Emeraldine base polyaniline can be used not only for anti-corrosion coatings, but also for the preparation of electromagnetic interference (EMI) shielding coatings and anti-static coatings.
The conductivity of polymers enables coatings to passivate exposed metal areas, while the principle of EMI shielding is to use low resistance conductor materials and utilize the reflection of electromagnetic waves on the shielding conductor surface, absorption inside the conductor, and loss during transmission to hinder their propagation. When conductive PAn is used as a conductor material, it can to some extent solve the disadvantages of expensive, high-density, and easily oxidized or corroded metal conductive fillers. Someone has prepared EMI shielding coatings by encapsulating carbon based materials with conductive PAn as the main conductive component and thermoplastic resin as the main film-forming substance.
The anti-corrosion mechanism of polyaniline is not yet clear, and researchers have proposed many theories, including shielding mechanism, electric field mechanism, bipolar coating mechanism, adsorption mechanism, anodic protection mechanism, dopant ion corrosion inhibition mechanism, and cathodic protection mechanism. It can be confirmed that during the transition of oxidation states, the oxidation-reduction potential of polyaniline is much higher than that of metals, which is one of the reasons why polyaniline has the ability to resist corrosion from metals.
Polyaniline has fully oxidized (LEB) and semi oxidized (EB) structures when the environmental pH value is ≥ 7. These two structures of polyaniline only play a mechanical isolation role in the protection process of metals, similar to the form of non-metallic coating protection on metal surfaces.
When polyaniline on the metal surface has defects, it does not provide protection to that area; When the environmental pH value of polyaniline is less than 7, the structure of polyaniline changes and forms the polyaniline salt (ES) form. At this time, polyaniline has good conductivity and electrochemical activity. This form of polyaniline not only has a mechanical isolation effect in metal protection, but also has a certain catalytic passivation effect.
When the polyaniline on the metal surface is damaged, it acts as a catalytic passivation agent on the affected area, causing the exposed metal part of the damaged polyaniline coating to undergo anodic oxidation reaction under acidic conditions, rapidly restoring the surface passivation layer.
Someone has used a composite coating material of polyaniline/polymethyl methacrylate for detecting low concentration ammonia gas. Based on the different conductivity of the composite material, the limit concentration of ammonia gas can be detected within the range of (10-4000) × 10-6. And when nitrogen is filled in, the conductivity and transmittance of the composite coating can quickly return to their initial state, thus achieving cyclic use.
battery
Polyaniline has the characteristics of high ability to store charges, good stability to oxygen and water, good electrochemical performance, low density, and reversible oxidation/reduction properties. It can be used as both a conductive matrix and an active material in composite electrodes, and has been used as electrode materials in polymer lithium batteries and solar cells.
The plastic battery made of emeraldine base polyaniline is not only lightweight, but also has a coulombic efficiency of over 95%. Its theoretical energy density can reach over 500Wh/kg, which is several times that of lead-acid batteries (184Wh/kg). Polymer lithium batteries, also known as lithium-ion batteries using PAn and PAn composites as electrode materials, mainly utilize the reversibility of doping/dedoping of PAn composites in the electrode reaction process to achieve redox reactions and complete the charging and discharging process of the battery. This battery has a high energy density and breaks through the problem of limited selection of positive electrode materials in traditional lithium-ion batteries.
PAn/V2O5 nanofibers were prepared by reverse micelle method and used as cathode materials for lithium-ion secondary batteries, and their electrochemical properties were studied. The results showed that composite nanofibers have better cycling performance than V2O5 nanofibers, and using carbon materials instead of metallic lithium as the negative electrode of batteries can replace the deposition and dissolution reactions of metallic lithium on the electrode, avoiding the problem of lithium dendrite formation on the negative electrode surface, maintaining the advantages of high voltage and high specific energy of lithium batteries, and greatly improving the cycling life and safety performance of batteries.
The basic mechanism of polymer solar cells is mainly based on the photovoltaic effect of semiconductor p-n junction, which means that under the irradiation of light, the electron hole pairs generated inside the semiconductor are separated and generate electromotive force under the action of electrostatic field. Polymer solar cells have the advantages of easy preparation and purification, easy processing, low cost, chemical modification according to needs, high open circuit voltage, and the ability to produce large-area flexible devices due to polymer semiconductor materials.
Absorber
The absorption principle of absorbing materials is to absorb or attenuate incident electromagnetic waves, and convert electromagnetic energy into thermal energy or other forms of energy for dissipation. Polyaniline is a type of electrical loss absorbing material, and its absorbing performance is closely related to its dielectric constant, conductivity, and other properties. Among them, PAn has a two electron conjugated system, its conductivity can vary between insulators, semiconductors and metals.
And it has the characteristics of molecular design and synthesis, diversified structure, small density, wide absorption band, adjustable electromagnetic parameters, easy composite processing, etc., which avoids the shortcomings of poor performance of magnetic metal microwave absorbing materials such as anti-aging, acid and alkali resistance, spectrum characteristics, etc. But PAn has strong inter chain rigidity and high brittleness, which can be improved by compounding it.
Someone has prepared DBSA doped PAn/MMTNCs, which exhibit microwave absorption performance in the range of 2-18 GHz. The reflection loss is less than -10 dB in the range of 13-14 GHz, and the maximum reflection loss at 13 GHz is -10.3 dB. The United States and other countries have already used it as a long-distance heating material for plastic welding technology in space shuttles. Polyaniline composite was also used to make radar absorbing materials with optical transparency, which were sprayed on the optical transparent windows of aircraft cockpit covers and precision guided weapons to weaken the radar echoes of targets.
However, it is difficult for PAn to simultaneously meet the characteristics of impedance matching and strong absorption, but it can be achieved by combining PAn with magnetic particles with magnetic loss absorption properties. For example, when nano NiFe2O4 crystals are added to a mixed system of PAN and paraffin, the composite powder mixture of PAn/NiFe2O4 and paraffin has both dielectric loss and magnetic loss within the test frequency range, and its microwave absorption performance in the mixed system is higher than that when PAN is added alone.
sensor
Due to its excellent conductivity, PAn can be used as a "molecular wire" to directly transfer electrons between bioactive substances and electrodes, significantly improving the response characteristics of biosensors and thus making third-generation biosensors without mediators. Moreover, by doping different anions during the synthesis process, it can be used to detect different analytical objects. Someone assembled a selective dopamine biosensor using droplet coating method, which can detect dopamine at a concentration of 1/5000 of vitamin C concentration in neutral.
Some people have used the color changing properties of polyaniline for detecting C-radiation, and determined the functional relationship between radiation dose and absorption spectrum by measuring the UV visible absorption spectra of polyaniline films exposed to different doses of radiation.
Conductive fiber
The preparation of conductive fibers using emeraldine base polyaniline not only has excellent and long-lasting conductivity, but also easily adjusts the conductivity of the fibers by changing the concentration of doping acid, which is an excellent property that other fibers do not possess. Mixing a very small amount of conductive fibers in ordinary fibers can endow fiber products with sufficient anti-static properties, and the anti-static properties will not be affected by environmental humidity. Someone has oxidized and doped the fibers, resulting in conductive fibers with a specific resistance of 1.05 × 10-2 Ω cm.
Frequently Asked Questions
Can polyaniline conduct electricity?
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Polyaniline (PANI) is a semiflexible rod polymer that conducts electricity. PANI has a conjugated structure that induces conductivity in a doped state, where the dopants are usually acids, offering PANI conductivity.
What is the pH of polyaniline?
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Thin layers of polyaniline are suitable to measure optically the pH in the range of 2–12 in the near infrared region. The deposition of such layers is strongly facilitated by the use of solution-processable polyaniline. Previously unconsidered hysteresis effects are observed in the titration curves.
Is polyaniline soluble in water?
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Pure polyaniline (PAni) is insoluble in water. Water-soluble complexes of PAni with different of cellulose derivatives were successfully synthesized by using chemical oxidation polymerization of aniline in aqueous solution of cellulose derivatives.
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