Innovation in the production of composite materials: the use of graphene in pultrusion

Innovation in the production of composite materials:

the use of graphene in pultrusion

Fiber-reinforced polymeric composites are widely used in the aerospace, automotive, naval, and wind power generation sectors due to their lightweight properties and high mechanical strength. These materials are a booming alternative to replace other materials such as metals.

At present there are different methods for the manufacture of fiber-reinforced composites, among which the pultrusion method stands out. A highly efficient and automated method that allows control of process parameters (greater precision and accuracy), reducing variability in the production of parts.

Pultrusion is a production process for reinforced materials where two components can be distinguished, the matrix or continuous phase and the reinforcement or discontinuous phase. The matrix acts as a bonding agent, in which the reinforcement is embedded. The function of the matrix is to transfer the load to the fibers, keep the fibers in their position, prevent the propagation of cracks, provide physical and chemical properties of the composite and also define the temperature range that the composite material can withstand. The matrix is thermosetting or thermosetting (unsaturated polyester, epoxy resins or vinyl-ester resins). On the other hand, the reinforcement has the purpose of adding some property that the matrix does not have, such as increasing mechanical resistance, rigidity, resistance to abrasion or improving its performance when exposed to high temperatures. The reinforcement efficiency is greater, the smaller the size of the particles or the diameter of the fiber and the more homogeneously they are distributed in the matrix. The most used fibers are glass, carbon and aramid due to their high tensile strength.

The pultrusion process (Figure 1) is continuous and is used to manufacture parts with a constant cross section, such as poles, rods, automotive moldings, etc. In the first feeding stage, the reinforcing fibers go through a perforated plate for alignment, then they go through a pre-molding where a fabric is added to reinforce the fiber. Later, in the second stage, the fibers are impregnated with liquid resin and go to a pre-forming stage where the fibers are oriented before entering the mold. In the third stage (molding), the cross section of the part is shaped, and the resin is hardened by applying heat. During the application of heat in the mold, there are three phases: pre-heating of the matrix and reinforcement, activation of the polymerization catalyst and curing of the material. The profile then exits the mold as a thermoset material and passes into a continuous traction mechanism that pulls the material at a constant speed (fourth stage)). Finally, in the fifth stage, a disk saw cuts the profile to the desired length. The profile of the reinforced composite obtained is a completely rigid material, which does not soften and is insoluble with the ability to withstand high temperatures.

Figure 1. General scheme of the pultrusion process: (1) Feeding, (2) Impregnation, (3) Molding, (4) Traction device and (5) Saw (Cutting).

Currently, the main applications of this process are focused on the manufacture of materials for construction, transport, and consumables, for example: vehicle construction, thermal insulation, cable ducts, covers and grids for water treatment plants, beam profiles, building facades, windows, bridges, stairs, among others.

However, there are still limitations in this technology, the low chemical interaction of the fiber with the matrix (resin) leads to a weak interface bond strength between both phases (low chemical adhesion), which makes the behavior of interlaminar shearing and performance of composite materials is not entirely satisfactory. In other words, if the matrix is brittle, spontaneous rupture can be generated. This behavior makes it possible to measure the resistance to interlaminar shearing. Depending on the type of break, the resistance of the matrix material or the quality of the fiber-matrix bond can be characterized.

In recent years, it has been reported that the introduction of functionalized graphene oxide (GO) on the surface of the fibers is an effective method to improve the interfacial properties of composite materials, since the large surface area of graphene oxide allows covering the surface of the fibers, increasing the strength of the chemical bond between the fiber and the matrix, thus improving the mechanical resistance of the reinforced composites. In addition, graphene oxide helps to improve the resistance to interlaminar fracture of the composite material, inhibiting the initiation and propagation of cracks.

The addition of graphene oxide to reinforced polymeric composites offers numerous advantages for the development of advanced materials in a wide variety of applications due to its large surface area, which has a strong impact on mechanical strength properties, greatly improving properties such as modulus, toughness, and fatigue. On the other hand, graphene oxide can provide compounds with greater resistance to fire. Its efficiency is associated with the fact that graphene oxide has a strong barrier effect, high thermal stability, and great surface absorption capacity, which are favorable for effectively reducing heat and mass transfer.

Currently, EnergeiaGraphenemex®, a leading Mexican company in Latin America in the research and production of graphene materials for the development of applications at an industrial level, sells graphene and graphene oxide that can be incorporated or dispersed in any matrix (resin) during the pultrusion process and with them improve the mechanical properties of the profiles or products.

The incorporation of graphene materials (graphene, graphene oxide) in the pultrusion process, provide improvements in the characteristics of the final product, which include:

  • Greater tensile strength. Tensile strength can increase up to 30% compared to a standard profile without graphene.
  • Production of lighter weight profiles since graphene allows the weight of the product to be reduced without affecting its mechanical properties.
  • Profiles with higher modulus of elasticity.
  • Greater resistance to corrosion and fire-retardant properties.
  • Greater resistance to fractures or fissures.

References

  1. Yuxin He, Qiuyu Chen. Effect of multiscale reinforcement by fiber surface treatment with polyvinyl alcohol/graphene oxide/oxidized carbon nanotubes on the mechanical properties of reinforced hybrid fiber composites. Composites Science and Technology 204 (2021).108634.
  2. Jonas H. M. Stiller, Kristina Roder, David Lopitz. Combining Pultrusion with carbonization: Process Analysis and materials properties of CFRP. Ceramics 2023, 6. 330-341.
  3. Dittrich B, Wartig K-A, Hofmann D, Mu¨lhaupt R, Schartel B. Flame retardancy through carbon nanomaterials: carbon black, multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polym Degrad Stab 98:1495.

Graphene in protection against electromagnetic radiation

Graphene in protection

against electromagnetic radiation

The development of communication technology together with electronic devices has generated great concern regarding the electromagnetic radiation emitted by these technologies.

Electromagnetic radiation is a type of electromagnetic field, that is, a combination of oscillating electric and magnetic fields, which propagates through space carrying energy from one place to another. Electromagnetic radiation can manifest itself in various ways, such as radio waves, microwaves, infrared radiation, visible light, ultraviolet radiation, X-rays or gamma rays and correspond to different wavelengths, ranging from kilometers (radio waves) to the order of picometers (gamma rays). The full range of wavelengths is what is called the electromagnetic spectrum (Figure 1.).

Electromagnetic radiation can be high frequency (radiation from mobile and wireless telephones, radio frequencies, TV waves, microwaves, radar, satellite signals, Wi-Fi, Bluetooth) and low frequency (fields generated by cables or electrical consumers).

Heat and electromagnetic radiation (EM radiation) are unavoidable by-products in electronic devices, especially those that operate at high frequencies. As electronic devices get smaller, they operate at higher and higher frequencies, generating even more heat and electromagnetic waves.

High frequency electromagnetic radiation not only degrades the devices themselves (producing heat), but also tends to interfere with neighboring electronic devices and most importantly, it has an adverse effect on human health as it can cause many diseases, such as leukemia, miscarriages, and brain cancer.

Therefore, the blocking or protection (shielding) against electromagnetic radiation could be one of the solutions to minimize health risks and for the protection of electronic equipment and/or devices. Metals are natural electromagnetic blocking materials, capable of reflecting electromagnetic waves due to their free electrons, which explains their high electrical conductivity and low penetration depth. However, their heavy weight, cost and the susceptibility of metals to corrosion make their use limited if not impossible.

The use of conductive coatings or paints to block electromagnetic radiation is the most viable option to solve the problem. Graphene is currently the most revolutionary nanotechnological additive in the coatings industry. Because graphene has extraordinary properties, which include high electrical conductivity, high thermal conductivity, and mechanical resistance. In addition, it possesses other distinctive properties, including gas impermeability, chemical resistance, antibacterial potential, and large surface area.

The electrical conduction capacity and thermal conductivity of graphene can be exploited in the formulation of shielding coatings against EM radiation, since graphene forms a continuous network along the surface of the coating, creating homogeneous films that block radiation. electromagnetic radiation while dissipating excess heat. In recent studies, it has been reported that the incorporation of carbon-based nanostructures, such as graphene in coatings or paints, allows the development of coatings with high electrical conductivity for shielding or protection against electromagnetic interference (EMI). The way to act with respect to high frequency electromagnetic waves is by refraction. Electromagnetic waves will bounce (reflect) off the treated surface similar to the effect of a mirror with respect to light (See Fig. 2). The barrier-effect in the propagation could be attributed to the contribution coming from the reflection capacity, the absorption and multiple internal reflections. The shielding efficiency increases with the addition of a higher concentration of graphene in the polymeric matrix of the coating. These graphene coatings can block more than 99.98% of high-frequency electromagnetic radiation.

Figure 2. Percentage of Reflection, absorption and transmission of pristine epoxy (a) and epoxy with graphene (b).
Taken from Adv. Electron. Mater. 2019, 5. 1800558

These coatings against electromagnetic radiation can act for both high frequency and low frequency, with an excellent quality of attenuation (decrease in intensity of signals or electric waves) of up to 38 dB, with one hand, and 47 dB if applied. two hands.

Energeia – Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of applications at an industrial level, through its Graphenergy line, is constantly researching and developing new multifunctional coatings and currently has for sale a wide range of nanotechnological coatings with graphene. Shielding coatings against electromagnetic radiation are currently being developed and evaluated. Coatings with high electrical conductivity, to reduce high and low frequency electrical fields respectively. These coatings will also offer anticorrosive and antimicrobial protection. In addition, to provide high resistance to wear, resistance to UV rays, impermeability and extraordinary adhesion.

Referencias

  1. Suneel Kumar Srivastava, Kunal Manna, Recent advancements in the electromagnetic interference shielding performance of nanostructured materials and their nanocomposites: a review, Journal of Materials Chemistry A, 10.1039/D1TA09522F, 10, 14, (7431-7496), (2022).
  2. Kargar, F., Barani, Z., Balinskiy, M., Magana, A. S., Lewis, J. S., Balandin, A. A., Adv. Electron. Mater. 2019, 5, 1800558.
  3. Seul Ki Hong et al 2012 Nanotechnology 23 455704.
  4. Lekshmi Omana, Anoop Chandran*, Reenu Elizabeth John, Runcy Wilson. Recent Advances in Polymer Nanocomposites for Electromagnetic Interference Shielding: A Review. Omega 2022, 7, 30, 25921–25947

Improve safety with flame retardant polymeric compounds with graphene oxide

Improve safety with flame retardant polymeric compounds

with graphene oxide

Polymeric compounds (engineering plastics) are widely used in the automotive, construction, food, aerospace and other sectors. Its use is based on the weight/resistance ratio, physical stability, chemical resistance and corrosion resistance.

However, most polymers, due to their nature, are flammable and combustible. That is, they are materials that catch fire quickly when exposed to fire, undergoing degradation, Veo complicadoand releasing heat to later start the propagation of the flames. During the combustion of polymers, they release smoke (soot) and toxic gases that are a danger to the safety of human life and property.

Four key components are involved during the combustion of polymeric materials: heat, oxygen, fuel, and free radical reaction. Flame retardancy of polymeric composites can be achieved by inhibiting or perturbing one or more of these components.

In recent years, multiple investigations have been carried out to develop additives that help inhibit or reduce the flammability of polymers, these additives are known as flame retardants.

Conventional flame retardants can be classified into two main categories, based on their components: inorganic flame retardants and organic flame retardants. The first include hydroxide, metal oxide, phosphate, silicate among others. They have excellent thermal stability, are non-toxic, are low cost and do not produce pollution. However, inorganic flame retardants are limited by high loading, low compatibility, and aggregation. On the other hand, organic flame retardants include flame retardants containing halogens, phosphorous, phosphorous-nitrogen, etc. The latter have high efficiency and good compatibility with polymers. Their main disadvantage is that they are restricted because they can release toxic gases and be harmful during combustion, endangering the health of people and the environment.

Graphene oxide (GO) is currently the most novel nanomaterial for use as a flame retardant because it exhibits high efficiency as a retardant with low loads and is non-toxic. Its efficiency is associated with the fact that graphene oxide has a strong barrier effect, high thermal stability and great surface absorption capacity, which are favorable for reducing heat and mass transfer.

Graphene-based flame retardants can improve the flame resistance of polymers by inhibiting the two key terms: heat and fuel. More specifically, graphene oxide can function as a flame retardant in different synergistic ways.

  1. First of all, GO has a unique two-dimensional layer structure and can promote the formation of a continuous dense layer of carbon during the combustion process. Carbon can act as a physical barrier to prevent heat transfer from the heat source and delay the escape of products (pyrolysis) from the polymeric substrate.
  2. Second, GO has a large specific surface area and can effectively adsorb flammable volatile organic compounds or hinder their release and diffusion during combustion.
  3. Third, GO contains abundant reactive oxygen-containing groups (carboxyl group at the edges, as well as epoxy and hydroxyl groups at the basal planes in the sheets). For example, oxygen-containing groups can undergo decomposition and dehydration at low temperatures, thus absorbing heat and cooling the polymeric substrate during combustion. Meanwhile, the gases generated by dehydration can dilute the oxygen concentration around the ignition periphery, decreasing the risk of fire spread.
  4. It can also modify the rheological behavior of the polymer and prevent its dripping, thus hindering the release and diffusion of volatile decomposition products through the ”maze effect” and affecting the flame retardancy of compounds (for example, modifying the UL-94 classification, oxygen index (OI) and time to ignition (TTI).

In studies carried out, it has been found that the incorporation of functionalized graphene oxide (5% by weight) in Polypropylene (PP) increased the Young’s modulus and the elastic limit of PP by 53% and 11%, respectively. While in the results of the flammability test (UL-94), it indicates that the presence of GO produces a change in the behavior of the melt and prevents the material from dripping.

On the other hand, the preparation of polymeric compounds in melt blending (extrusion) of Polystyrene/GO have been reported, where it was found that GO (5%) can promote carbonization on the polymer surface (layer of carbonized material). and inside, the presence of a load or filler that presents high resistance to heat and contributes to the formation of carbon residues, improving the flame resistance of polystyrene-based compounds.

Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of applications at an industrial level, through its Graphenergy Masterbatch line, has developed a wide range of masterbatches with graphene oxide, based on various polymers, such as PP, HDPE, LDPE, PET and PA6.

The incorporation of graphene and graphene derivatives (GO) to polymeric matrices has allowed the development of polymeric compounds with better mechanical properties, greater thermal stability, gas barrier capacity and reduced flammability of polymeric compounds.

References

  1. Han Y, Wu Y, Shen M, Huang X, Zhu J, Zhang X. Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants. J Mater Sci 48:4214.
  2. Hofmann D, Wartig K-A, Thomann R, Dittrich B, Schartel B, Mu¨lhaupt R. Functionalized graphene and carbon materials as additives for melt-extruded flame retardant polypropylene. Macromol Mater Eng 298:1322.
  3. Dittrich B, Wartig K-A, Hofmann D, Mu¨lhaupt R, Schartel B. Flame retardancy through carbon nanomaterials: carbon black, multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polym Degrad Stab 98:1495.

Innovation in the plastics industry: how graphene masterbatches are changing the game

Innovation in the plastics industry:

how graphene masterbatches are changing the game

Graphene has extraordinary electrical, optical, thermal properties and high mechanical resistance. The properties of graphene are attributed to its structure in the form of two-dimensional (2D) sheets, formed by hexagonal bonded carbon atoms and a thickness of one carbon atom.

Today, graphene is the most promising nanotechnological additive in the plastics industry. The incorporation of graphene and its derivatives (graphene oxide, GO) in different polymer matrices (masterbatches), have great potential for a wide range of applications. The graphene masterbatch can act as a mechanical reinforcement or conductive additive for both thermoplastic and thermosetting materials. They can be used in the automotive, aerospace, electronics or packaging sectors.

Graphene-based polymeric compounds have shown significant improvements in properties such as elastic modulus, tensile strength, impact resistance, electrical conductivity, resistance to UV radiation, thermal stability, antimicrobial property, impermeability or barrier effect (it does not allow the diffusion of moisture or other molecules).

Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of applications at an industrial level, through its Graphenergy Masterbatch line, has developed and sells a wide range of masterbatches with graphene, based on various polymers, such as PP, HDPE, LDPE, PET and PA6.

Our Masterbatches are granular materials that act as multifunctional additives. The incorporation of graphene in different polymer matrices has shown important effects on the properties and processing conditions of plastics, among which are:

  • Increased resistance to tension, deformation and impact
  • Increased resistance to ultraviolet rays
  • Excellent dispersion
  • Improves processing conditions (thermal stability)
  • Acts as a nucleating agent (modification of the crystallization temperature of the polymer)

In this sense, it has been found that the incorporation of graphene and its derivatives, as well as the concentration, can modify the physicomechanical properties of the polymer to be processed. The addition of masterbatch to different polymers has improved the final characteristics of the material to a lesser or greater extent, for example:

  • Additivation of Polypropylene (PP) with polypropylene-graphene masterbatch (MB-PP/GO), increases tensile strength (8%) and rupture percentage (29%).
  • Additivation of Polyethylene (PE) with polyethylene-graphene masterbatch (MB-PE/GO), improves tensile strength (17%), flexural strength and rupture strength (66%).
  • Additivation of Polyethylene terephthalate (PET) with polyethylene terephthalate-graphene masterbatch (MB-PET/GO), improves resistance to humidity, increases tensile strength (72.2%) and improves impact resistance.
  • Additivation of Polycarbonate (PC) with polycarbonate-graphene masterbatch (MB-PC/GO), improves resistance to humidity and improves resistance to rupture (276%).

On the other hand, graphene masterbatches can also be incorporated into recycled polymers. Currently, the reuse and recycling of plastic materials are of vital importance in the transition path towards a circular economy. In this regard, the constant washing, pelletizing and reprocessing can cause the loss of physicomechanical properties of recycled plastics, therefore, by adding graphene, these properties can be restored or improved. In agricultural applications, mulch films with increased resistance to ultraviolet radiation can be produced.

References

  1. Fang, M., et al., Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites. Journal of Materials Chemistry. 19(38): p. 7098-7105.
  2. Kim, H., A.A. Abdala, and C.W. Macosko, Graphene/Polymer Nanocomposites. Macromolecules. 43(16): p. 6515-6530.
  3. Balandin, A.A., et al., Superior Thermal Conductivity of Sin gle-Layer Graphene. Nano Letters, 8(3): p. 902-907.
  4. Nabira Fatima, Umair Yaqub Qazi, Asim Mansha., Recent developments for antimicrobial applications of graphene-based polymeric composites: A review, https://doi.org/10.1016/j.jiec.2021.04.050

Innovation in corrosion protection: graphene oxide technology

Innovation in corrosion protection:

graphene oxide technology

Corrosion is the greatest challenge that many industries in the world must face. Currently, there is a wide variety of coatings on the market for protection against corrosion. However, most of these coatings do not have the physicochemical characteristics necessary for good performance. These coatings does not have perfect barriers and eventually fail, their chemical resistance depends on their impermeability to chemical substances, and with it their resistance to abrasion and their adhesion capacity.

Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in the research and production of graphene materials for the development of industrial applications, has a wide range of coatings through its Graphenergy line.

Graphenergy is the line of nanotechnological coatings with graphene oxide, which has a complete portfolio of high-performance anticorrosive coatings for Industrial and Infrastructure maintenance.

Taking into account that the infrastructure or industrial equipment may be exposed to environments with different degrees of corrosion (intermediate or extreme), the use of Coating Systems for corrosion protection is recommended, Graphenergy offers the following alternatives:

1. ALKYD SYSTEM

Recommended for intermediate or mild corrosion environments (intermediate corrosive or aggressive conditions). This system is weather resistant and provides anticorrosive protection.

This system is made up of a primer and alkyd-type enamel, ideal for the protection of metal surfaces and industrial infrastructure, both for interiors and exteriors. Provides high anticorrosive protection, resistance to UV rays and provides extraordinary adherence to the substrate. It is recommended for non-coastal areas or where humidity conditions are not high.

2. EPOXY-POLYURETHANE SYSTEM

Designed for severe or critical environments, in which the infrastructure or equipment and/or some other protected element is exposed to UV rays and an industrial atmosphere with high contamination (highly corrosive vapors).

This system is made up of an epoxy primer and Polyurethane (finish). Coatings designed for the protection of metal surfaces exposed to highly corrosive and chemical environments. Both coatings offer high adhesion, extraordinary chemical resistance, high abrasion resistance, resistance to UV rays, and impermeability, to improve the life of any metal surface or installation and reduce maintenance costs.

Graphenergy anticorrosive coating systems have many benefits, which include:

  • Higher performance than existing coating technologies on the market today.
  • Fewer applied coating layers are required and with higher anti-corrosion protection.
  • Coatings with greater adherence to the substrate.
  • Coatings with greater chemical resistance and high thermal resistance.
  • Coatings with greater impermeability and non-stick effect.

When a coating system is selected, the influence of the environment to which it will be exposed and the final appearance that is sought and some other considerations that the system must perform, and its maintenance must be taken into account.

On the other hand, another decisive factor that determines the selection of the first anticorrosive to be used and consequently the coating system is the physical state of the metal surface to be coated and/or the surface treatment or preparation that can be given.


Referencias

  1. Fengjuan Xiao, Chen Qian, et al., et al., Progress in Organic Coatings, 125, 79-88 (2018); doi.org/10.1016/j.porgcoat.2018.08.027
  2. Karolina Ollik and Marek Lieder. Review of the application of graphene-based coatings as anticorrosion layers. Coatings 2020, 10(9), 883. 2020.
  3. Zhang J., Kong, G., Li S., Le Y., Che C., Zhang S., Lai D., Liao X. Graphene-reinforced epoxy powder coating to achieve high performance wear and corrosion resistance. 20:1448-4160, 2020.

Graphene oxide: the new ally of primary coatings in corrosion protection

Graphene oxide:

the new ally of primary coatings in corrosion protection

Corrosion is an electrochemical reaction that occurs when the metal reacts with the surrounding environment forming ferric oxide, causing the metal to lose its main characteristics of hardness and resistance. Oxygen, temperature, humidity, contaminants, gases, and the physicochemical characteristics of water are the main factors that affect the rate at which metals corrode.

One of the most widely used methods to control corrosion is the application of protective (primer) coatings to metal surfaces. The coating forms a barrier between the substrate (metal) and the surrounding medium, retarding the deterioration or oxidation of the metal. The coatings are polymer-based substances (paints), resistant to degradation, which are used to cover the material to be protected.

Nowadays, a wide variety of primers have been developed based on different types of resin, such as the alkyd and epoxy type. Efficiency is generally associated with an increase in cost. Unfortunately, most of these coatings or paints are not perfect barriers and eventually fail due to holes or micropores in the coating or the diffusion of oxygen and water through it (they are not completely waterproof). On the other hand, the coatings continue to have low thermal resistance and above all a limited chemical resistance.

Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in the research and production of graphene materials for the development of industrial applications, through its Graphenergy line, has launched a range of primers and other nanotechnological coatings.

Graphenergy anticorrosive primers are coatings based on graphene oxide (GO), a new nanotechnological additive that provides multiple properties to coatings, including extraordinary corrosion protection and barrier technology (barrier effect). Graphene oxide creates pathways that are very tortuous, which prevents oxygen and water molecules from diffusing through the coating and eventually reaching the metal surface, providing protection against corrosion (Fig. 1). These primaries can act as mentioned, by (1) forming a barrier, which greatly prevents the penetration of oxygen and water molecules, or (2) the inhibition of the corrosion process, by increasing the electrical and ionic resistivity, cutting the corrosion cycle.

Fig. 1 Mechanism of anticorrosive protection of coatings based on polymers and graphene.

Among the anticorrosive primers that are currently for sale by Graphenergy, there are two: “Graphenergy anticorrosive alkyd primer” and “Graphenergy anticorrosive epoxy primer”, each one designed according to different needs and conditions.

A. Graphenergy anticorrosive alkyd primer.

Provides high anticorrosive protection, resistance to UV rays and provides extraordinary adherence to the substrate. Ideal for the protection of industrial infrastructure, for the application of ferrous surfaces, both for interiors and exteriors. It is recommended for non-coastal areas or where humidity conditions are not high.

B. Graphenergy anticorrosive epoxy primer.

In addition, this coating offers extraordinary chemical resistance, with high wear resistance, resistance to UV rays, impermeability and greater adhesion, in order to improve the useful life of any metal surface or installation and reduce maintenance costs.

Graphene coatings provide enhanced properties and many more benefits, including:

  • Higher performance than existing coating technologies on the market today.
  • Fewer applied coating layers are required and with higher anti-corrosion protection.
  • Zinc reduction in formulations can reduce the amount by up to 50%.
  • Primers with greater chemical resistance and high thermal resistance.
  • Coatings with greater impermeability and non-stick effect (dirt does not adhere to it). Graphene oxide creates a two-dimensional network on the surface of the coating, which does not allow the anchoring or diffusion of water molecules or chemical substances, which allows the development of coatings with a hydrophobic effect, resulting in coatings that are easier to clean (See Fig.2).
Fig. 2. Behavior of coatings without and with graphene oxide, after subjecting them to a chemical attack (corrosive solution) for more than two hours.
  • Improves adhesion to the substrate. The primers with graphene oxide increase their adherence by up to 50% with respect to the control (Fig. 3).
Fig. 3. Primer adhesion test with and without graphene oxide.
  • More flexible coatings. The incorporation of graphene oxide not only improves adhesion, but also allows flexibility to the coating, allowing it to have high resistance to bending or greater resistance to fracture (Fig. 4).
Fig.4. Flexibility test in primary without and with graphene oxide.

Referencias

  1. Chang, C.-H. et al. Novel Anticorrosion Coatings Prepared from Polyaniline/Graphene Composites. Carbon N. Y. 50, 5044–5051 (2012).
  2. Fengjuan Xiao, Chen Qian, et al., et al., Progress in Organic Coatings, 125, 79-88 (2018); doi.org/10.1016/j.porgcoat.2018.08.027
  3. Karolina Ollik and Marek Lieder. Review of the application of graphene-based coatings as anticorrosion layers. Coatings 2020, 10(9), 883. 2020.
  4. Zhang J., Kong, G., Li S., Le Y., Che C., Zhang S., Lai D., Liao X. Graphene-reinforced epoxy powder coating to achieve high performance wear and corrosion resistance. 20:1448-4160, 2020.
  5. Ghosh Tuhin and Karak Niranjan. Mechanically robust hydrophobic interpenetrating polymer network-based nanocomposites of hyperbranched polyurethane and polystyrene as an effective anticorrosive coating. New J. Chem., 2020, 44, 5980-5994.

Nanotechnology and corrosion protection: the era of graphene oxide

Nanotechnology and corrosion protection:

the era of graphene oxide

Corrosion is defined as the gradual deterioration of metallic materials and their properties, and occurs when the metal reacts with the surrounding environment to form rust or another chemical compound. In general, atmospheric air, humidity, rain, and aqueous solutions (chemical products) are the environments that are most frequently associated with corrosion problems.

Nowadays, corrosion damage is one of the most important problems to face for many industries in the world. It is estimated that corrosion causes economic losses of 3.4% of world GDP (about 2.5 billion dollars per year). However, there are three industries whose corrosion impact is more frequent and riskier for their processes: the chemical industry, the shipbuilding industry and the construction industry.

In the chemical industry, the use of chemical products is paramount within its operations, so equipment and machinery are in direct and constant contact with chemical substances, increasing maintenance and/or repair costs, affecting the industry budget and their production. In the case of the naval industry, humidity and salt are the main factors that contribute to the corrosion process and, consequently, the deterioration and affectation of its facilities, ships, containers and even merchandise. On the other hand, in the construction industry, both the machinery and the construction areas themselves can be affected by corrosion due to their exposure to the environment. Corrosion causes the metallic assets to weaken, generating mechanical failures, putting the work at risk.

Anticorrosive coatings are regularly used for protection against corrosion, humidity and fouling of installations, machinery and equipment. At a commercial level, there is a wide variety of anticorrosive coatings based on different additives and resins, their efficiency is generally associated with an increase in cost. However, the coatings still have low thermal and corrosion resistance and especially limited chemical resistance.

Graphene is currently the most revolutionary nanotechnological additive in the coatings and paints industry. The incorporation of graphene as an additive in coatings produces coatings with extraordinary protection against corrosion. Graphene creates pathways that are very tortuous, preventing water and oxygen molecules and/or chemical agents from diffusing to the surface of metal-based materials, resulting in metal protection against oxidation and corrosion. corrosion (Fig. 1).

Figure 1. Schematic representation of the tortuous path for oxygen and water molecules in polymer coatings with clay and graphene.

Graphene coatings provide many performance and anti-corrosion benefits, including:

  • Higher performance than existing coating technologies on the market today.
  • Fewer applied coating layers are required for greater benefits
  • Zinc reduction in formulations
  • Chemical resistance


Graphene and graphene oxide-enhanced anticorrosive coatings will replace traditional zinc-based coatings, which have several drawbacks, such as short life, high content of volatile organic compounds (VOCs), slow curing, high cost, sedimentation in storage.


Currently Energeia – Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of industrial applications, through its Graphenergy line, has launched a wide range of nanotechnological coatings with graphene. These coatings offer high anticorrosive protection, extraordinary chemical resistance, high wear resistance, resistance to UV rays, impermeability and greater adherence, in order to improve the useful life of any surface or installation and reduce maintenance costs.

References

  1. Chang, C.-H. et al. Novel Anticorrosion Coatings Prepared from Polyaniline/Graphene Composites. Carbon N. Y. 50, 5044–5051 (2012).
  2. Fengjuan Xiao, Chen Qian, et al., et al., Progress in Organic Coatings, 125, 79-88 (2018); doi.org/10.1016/j.porgcoat.2018.08.027
  3. Chaudhry, A. U., Mittal, V. & Mishra, B. Inhibition and Promotion of Electrochemical Reactions by Graphene in Organic Coatings. RSC Adv. 5, 80365–80368 (2015).
  4. Zhen, Z. & Zhu, H. Graphene: Fabrication, Characterizations, Properties and Applications. Graphene (Academic Press, 2018).

Protection against bacteria, viruses and fungi with graphene coatings

Protection against bacteria, viruses and fungi

with graphene coatings

In less than 20 years the world has faced a series of abnormal phenomena caused by highly infectious pathogens. The easy and rapid transmission of infections forces us to seek increasingly efficient strategies to strengthen health services, in addition to representing a radical change in our lifestyle, where extreme hygiene techniques are in first place of importance to avoid the spread and massive contagion inside and outside hospitals.

Viral diseases of greater impact.

  • 2002-2003. Severe acute respiratory syndrome (SARS-Cov).
  • 2012. Middle East Respiratory Syndrome (MERS-Cov).
  • 2014- 2016. Ebola.
  • 2019- 2022. SARS-Cov-2.

>6.5 million deaths.

Dangerous bacteria for human health:

  • Staphylococcus aureus.
  • Streptococcus pneumoniae.
  • Pseudomonas aeruginosa.
  • Haemophilus influenzae.
  • Helicobacter pylori.

Common fungi in the domestic environment:

  • Aspergillus spp.
  • Cladosporium spp.
  • Alternaria spp.
  • Acremonium spp.
  • Epiccocum spp.
  • Penicillium spp.
  • Stachybotrys spp.

Graphene as an adjuvant in infection control

In 2018, Energeia- Graphenemex® launched the antimicrobial Graphenergy line, made up of two specialized vinyl- and vinyl-acrylic-based coatings with graphene oxide, whose antimicrobial potential is 400 times higher than common products, helping to keep surfaces free of fungi and bacteria for a long time.

In vitro studies and in a relevant environment carried out by the Laboratory of Pathology, Biochemistry and Microbiology of the Faculty of Stomatology of the U.A.S.L.P., showed that surfaces protected with antimicrobial Graphenergy remain free of microorganisms for more than 6 months, without the need for additional chemicals. Figure 1.

Fig. 1. Results at 2, 4 and 6 months on the protection of antimicrobial Graphenergy compared to a control group (No Graphene Oxide).
Important: A clean surface is in the range of 1-10 CFU/cm2.

In 2022, the strategic alliance between the companies Energeia-Graphenemex® and Oxical® is preparing to launch a new 100% natural coating, without toxic compounds (VOCs), highly waterproof, breathable and highly antimicrobial, made from high-quality and purity lime modified with Graphene nanoparticles, under the ecological Graphenecal brand.

Its extraordinary antimicrobial capacity is not only a great aid in keeping spaces free of microorganisms, but also protects surfaces against biodeterioration, particularly those with high historical value. Figure 2.

Fig. 2. Graphene-free lime paint has a microbial biofilm on more than 90% of its surface. The area covered with organic Graphenecal remained free of contamination for more than 100 days of incubation. The antimicrobial effect of organic Graphenecal is highly effective, with a reduction of microorganisms of 7 Log10.

Is graphene nanotechnology safe?

Yes, Graphenergy and Graphenecal antimicrobial coatings are as safe as any conventional paint or coating. The graphene and graphene oxide nanoparticles contained in its formulations do not shed or release toxic substances into the environment.

“Not all microorganisms are dangerous, but it is better to keep them away”

How do graphene materials work?


  1. Physical barrier- High impermeability. Graphene materials are usually presented in millions of blocks composed of 1 to 10 nanometric sheets similar to a pack of cards, with multiple sinuous paths between each sheet that act as an external barrier that suppresses the entry of essential nutrients for microbial growth.

  2. Graphene and its derivatives can act as electron donors or acceptors, altering the respiratory chain of the microorganism or extracting its electrons. This imbalance in the form of a nano-circuit is so fast that it does not give the microorganism time to recover and, therefore, inactivates it before adhering to the surface.

  3. Structural damage. The edges of the nanomaterial sheets act like small knives that damage or break the cell membrane of the microorganism, altering its functioning and preventing its viability.

Do graphene materials have antiviral activity?

The antiviral effect of graphene materials seems not to be very different from that described against fungi and bacteria. The hypotheses are directed towards an interesting synergistic effect between impermeability, structural damage and electrostatic interactions due to the positive polarity of some viruses (SARS-Cov-2) and the negative polarity of graphene oxide, in addition to its great protein-anchoring capacity.

Energeia- Graphenemex®is the pioneer Mexican company in Latin America focused on the research and production of graphene materials for the development of applications at an industrial level. In addition to adding value to its products with the multifunctional properties of Graphene and its derivatives, the company also aims to create strategic alliances to support innovative developments with graphene nanotechnology.

References

  1. García-Contreras R, Guzmán Juárez H, López-Ramos D & Alvarez Gayosso C. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1-9. Doi:10.17126/joralres. 2021.019
  2. UM.D. Giulio, R. Zappacosta, S.D. Lodovico, E.D. Campli, G. Siani, A. Fontana, L. Cellini, Antimicrobial and antibiofilm eficacy of graphene oxide against chronic wound microorganisms. Antimicrob. Agents Chemother. 62(7), e00547-18 (2018). https://doi.org/10.1128/AAC.00547-18
  3. H.E. Karahan, C. Wiraja, C. Xu, J. Wei, Y. Wang, L. Wang, F. Liu, Y. Chen, Graphene materials in antimicrobial nanomedicine: current status and future perspectives. Adv. Healthc. Mater. 7(13), 1701406 (2018). https://doi.org/10.1002/ adhm.201701406
  4. Sydlik SA, Jhunjhunwala S, Webber MJ, Anderson DG, Langer R. In vivo compatibility of graphene oxide with differing oxidation states. ACS Nano. 2015. 9: 3866
  5. Yang K, Zhang S, Zhang G, Sun X, Lee ST, Liu Z. Graphene in mice: ultrahigh in vivo tumor uptake and efficient photothermal therapy. Nano Lett. 2010. 10: 3318.
  6. Bhattacharya K, Farcal LR, Fadeel B. Shifting identities of metal oxide nanoparticles: focus on inflammation. 2014. MRS Bull; 39: 970
  7. Huang PJ, Pautler R, Shanmugaraj J, Labbé G, Liu J. Inhibiting the VIM-2 metallo-β-lactamase by graphene oxide and carbon nanotubes. ACS Appl Mater Interfaces 2015; 7: 9898.
  8. Moghimi SM, Wibroe PP, Wu L, Farhangrazi ZS. Insidious pathogen-mimicking properties of nanoparticles in triggering the lectin pathway of the complement system. Eur J Nanomedicine. 2015; 7: 263.
  9. Bhattacharya K, Mukherjee SP., Gallud A., Burkert SC., Bistarelli S., Bellucci S., Bottini, M., Star A., Fadeel B. Biological interactions of carbon-based nanomaterials: From coronation to degradation. Nanomedicine: Nanotechnology, Biology, and Medicine. 2016. 12. 333

Graphene oxide: a promising alternative in nanotechnology

Graphene oxide:

a promising alternative in nanotechnology

Since graphene was isolated for the first time in 2004 by the Manchester group, this nanomaterial has proven to be the most revolutionary for the development of new applications at an industrial level.

Graphene has extraordinary electrical, optical, thermal properties and high mechanical resistance. The properties of graphene are attributed to its structure in the form of two-dimensional (2D) sheets, made up of hexagonally bonded carbon atoms and a thickness of one carbon atom.

Currently there are different methods of graphene production, these can be classified into two methods, according to their origin, the “bottom-up” method and the “top down” method. The “bottom-Up” method consists in the creation of graphene structures through building blocks (atoms, molecules), for example, by Chemical Vapor Deposition (CVD); and the “top down” method involves the production of graphene from the oxidation of graphite. Graphite is made up of sheets of graphene that are stacked on top of each other. The following diagram represents the process for obtaining graphene from the oxidation of graphite.

Schematic diagram of the process for obtaining GO, through the oxidation of graphite.

The graphite oxidation process begins with the addition of graphite in sulfuric acid (H2SO4), with constant mechanical stirring. Subsequently, potassium permanganate (KMnO4) is slowly added, producing a chemical reaction that allows the graphite (graphene sheets stacked on top of each other) to be chemically modified in its structure. When KMnO4 reacts with H2SO4, it forms manganese oxide VII (Mn2O7), which is a very selective oxidizing agent on double bond aromatic compounds, such as graphite. The oxidizing agent molecularly attacks the structure of each graphene sheet in the graphite, grafting oxygenated functional groups (with oxygen), such as epoxide groups (C-O-C) and hydroxyl groups (-OH), on each sheet, and carboxyl groups (-COOH, CO2H ) on the edges of each sheet, obtaining graphite oxide and graphene oxide (GO), see Figure 1.

Figure 1. Structure of graphene oxide

The incorporation of oxygenated functional groups allows a material such as graphite, which is highly hydrophobic (which repels water) and a good electrical conductor, to become graphite oxide and graphene oxide (GO), highly hydrophilic materials, that is, they mix and disperse easily with water (See Figure 2). GO is chemically similar to graphite oxide, but structurally differs in the arrangement and number of stacked sheets.

The GO can be defined as a single exfoliated graphene sheet or stack of few sheets (3-4) that is functionalized with different oxygenated groups. Among its main characteristics is that it is hydrophilic, insulating and hygroscopic (absorbs moisture). On the other hand, graphene oxide sheets possess a large surface area and exhibit high mechanical strength and flexibility.

Applications

Graphene oxide has attracted great interest in various fields of science and technology, due to its remarkable mechanical, chemical, and thermal properties, among others. So numerous investigations began, to take advantage of the properties of graphene oxide.

In 2011, the first investigations of the use of GO as a precursor in the large-scale production of graphene emerged, for use as filler/reinforcement material/in polymeric matrices, such as high-density polyethylene (HDPE) and low-density polyethylene (HDPE). density (LDPE).

By 2014, GO was considered feasible for use as a flame retardant agent. Research is still ongoing to functionalize it with different polymeric materials.

In 2017, the first reports of the manufacture of GO-based membranes began, since it is impermeable to gases and liquids, showing its ability to filter small particles, organic molecules and even its use for seawater desalination.

In 2018, Energeia-Graphenemex started research on graphene oxide as a new additive for the production of anticorrosive and antimicrobial coatings. By 2019, studies of graphene oxide in coatings with antibacterial behavior increased, associated with the fact that GO is capable of penetrating the cell membrane of bacteria, producing oxidative stress and inhibiting their reproduction.

In particular, the functionalization of GO allows it to be applicable in biological systems, development of biosensors for the identification of specific molecules, drug delivery systems, among others.

Energeia Graphenemex®, a leading Mexican company in Latin America in research and production of graphene materials for the development of industrial applications. It has extensive experience in the production of graphene oxide (GO) on a large scale, with different degrees of oxidation and high quality for use in different applications and industries. Currently, it uses graphene oxide in the production of concrete additives and anticorrosive and antimicrobial coatings that are marketed under the Graphenergy brand.

References

  1. M. Fang, K. Wang, H. Lu, Y. Yang y S. Nutt, «Covalent polymer functionalization of graphene nanosheets and mechanical properties of composites,» Journal of Materials Chemistry, vol. 19, pp. 7098-7105, 2009.
  2. B. Dittrich, K.-a. Wartig, R. Mülhaupt y B. Schartel, «Flame-Retardancy Properties of Intumescent Ammonium Poly(Phosphate) and Mineral Filler Magnesium Hydroxide in Combination with Graphene,» Polymers, vol. 6, pp. 2875-2895, 2014.
  3. Y.-j. Wan, L.-x. Gong, L.-c. Tang, L.-b. Wu y J.-x. Jiang, «Mechanical properties of epoxy composites filled with silane-functionalized graphene oxide,» COMPOSITES PART A, vol. 64, pp. 79-89, 2014.
  4. J. Wang, C. Xu, H. Hu, L. Wan, R. Chen, H. Zheng, F. Liu, M. Zhang, X. Shang y X. Wang, «Synthesis , mechanical , and barrier properties of LDPE / Graphene nanocomposites using vinyl triethoxysilane as a coupling agent,» J. Nanopart Res, vol. 13, pp. 869-878, 2011.