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.

The safety of graphene in human health: what science says about it

The safety of graphene in human health:

what science says about it

Part II. Are graphene materials safe for humans?

The family of graphene materials comprises a wide range of two-dimensional (2D) carbon nanostructures in the form of sheets that differ from each other by the particularities derived from the production method or by the innumerable functionalizations that can be performed after its obtaining. In 2022, Nature magazine, one of the most important scientific journals in the world, published a study in which 36 products from graphene suppliers from countries such as the United States, Norway, Italy, Canada, India, China, Malaysia and England were analyzed, concluding that graphenes represent a heterogeneous class of materials with variable characteristics and properties, whether mechanical, thermal, electrical, optical, biological, etc., which can be transferred to a large number of three-dimensional (3D) compounds to modify or create new products.

“Undoubtedly, graphene and nanotechnology in general continue to be controversial issues as they confront us with a world that is difficult to see and understand, but with simply amazing effects”

Are graphene materials safe?

Graphene materials promise to be an important tool within biomedical technologies. In principle, its benefits can be used for the design of diagnostic elements such as sensors and devices for images up to neural interfaces, gene therapy, drug delivery, tissue engineering, infection control, phototherapy for cancer treatment, bioelectronic and dental medicine, among other. But for them to be truly used in this type of technology, their interactions with the biological environment must first be understood or, failing that, ensure that their presence does not alter the natural environment of the cells. In this sense, numerous studies have been carried out with the different forms, presentations, and available concentrations of graphene whose findings have gradually paved the way for its safe use in biomedical technologies:

i) Graphene materials in their free form. In in vitro tests, exposure of human lung epithelial cells to graphene sheets at concentrations lower than 0.005 mg/ml did not cause significant changes in their morphology or adhesion,2,3 nor was cytotoxic activity identified in stem cells derived from adipose tissue. human, periodontal ligament and dental pulp exposed to 0.5 mg/ml of GO,4 even and understanding a possible dose-size dependent effect, other investigations report safe concentrations below 40 mg/ml or, that do not exceed 1, 5% w/v. 5-8

Finally, one of the most recent in vivo studies published by the University of Manchester, United Kingdom, on the pulmonary response of mice exposed to graphene oxide (GO) in the respiratory tract, did not identify significant damage or pulmonary fibrosis at 90-day follow-up. These results provide solid grounds for the safety of these nanostructures without underestimating basic safety measures, such as avoiding their inhalation.9 Likewise, scientists from the University of Trieste, Italy, analyzed the impact of graphene materials on the skin, reporting low toxicity on cells.10

“It is unlikely that graphene materials in their free form are used to be in contact with the biological environment, they are generally functionalized or immobilized in other materials to develop an application”

ii) Functionalized graphene materials. Functionalization is the term that refers to the chemical modification of a nanomaterial to give it a “function”, that is, to facilitate its incorporation with other compounds or to benefit its biocompatibility and better direct its use by anchoring functional groups, molecules, or nanoparticles. A study published in the journal Nature Communications on graphene bioapplications highlights the importance of its functionalization with amino groups to make it more compatible with human immune cells.11,12

“The most common functionalization of graphene is the anchoring of oxygenated groups on its surface, this material is known as graphene oxide”

iii) Immobilization in polymers. The use of graphene materials as nano-filling for plastics, resins, coatings, etc., is the most common way in which these nanostructures are used. For the biomedical sector, its immobilization in polymers has shown good biocompatibility and stimulation of cell proliferation; antimicrobial activity and improvement of the mechanical properties of polymers, being classified as excellent candidates for the manufacture of bone fixation devices, molecular scaffolds, orthopedic implants, or dental materials.13-15

Given the great potential of graphene materials in health sciences, but also due to the many questions about their safety, an international research team from the European Graphene Flagship project, led by EMPA (German acronym for the Federal Institute for Testing and Materials Research), conducted a study to assess the potential health effects of graphene materials immobilized within a polymer; the results showed that the graphene particles released from said polymeric compounds after abrasion induce insignificant effects.16

“It is reassuring to see that this study shows negligible effects, confirming the viability of graphene for mass applications. Andrea C. Ferrari, Graphene Flagship Science and Technology Officer.” 17,18

Energeia-Graphenemex, the pioneering Mexican company in Latin America in the research and development of applications with graphene materials, throughout its 10-year career has overcome numerous scientific and industrial challenges to reach the market with products for industrial use. In 2018, it began to explore the antimicrobial capabilities of its products with excellent results in vitro and in a relevant environment; currently, and in conjunction with other research centers, it is carrying out evaluations to explore the potential of its materials as nano-reinforcement of biopolymers.

Drafting: EF/DHS

References

  1. Cytotoxicity survey of commercial graphene materials from worldwide. npj 2D Materials and Applications (2022) 6:65
  2. Biocompatibility of Pristine Graphene Monolayers, Nanosheets and Thin Films. 2014, 1406.2497.
  3. Preliminary In Vitro Cytotoxicity, Mutagenicity and Antitumoral Activity Evaluation of Graphene Flake and Aqueous Graphene Paste. Life 2022, 12, 242
  4. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1
  5.  Graphene substrates promote adherence of human osteoblasts and mesenchymal stromal cells. Carbon. 2010; 48: 4323–9
  6. Multi-layer Graphene oxide in human keratinocytes: time-dependent cytotoxicity. Prolifer Gene Express Coat 2021; 11:1
  7. Cytotoxicity assessment of graphene-based nanomaterials on human dental follicle stem cells. Colloids Surf B Biointerfaces. 2015; 136:791
  8. Arabinoxylan/graphene-oxide/nHAp-NPs/PVA bionano composite scaffolds for fractured bone healing. 2021. J. Tissue Eng. Regen. Med. 15, 322.
  9. Size-Dependent Pulmonary Impact of Thin Graphene Oxide Sheets in Mice: Toward Safe-by-Design. Adv. Sci. 2020, 7, 1903200
  10. Differential cytotoxic effects of graphene and graphene oxide on skin keratinocytes. 2017. Sci Rep 7, 40572
  11. Amine-Modified Graphene: Thrombo-Protective Safer Alternative to Graphene Oxide for Biomedical Applications. ACS Nano 2012, 6, 2731
  12. Single-cell mass cytometry and transcriptome profiling reveal the impact of graphene on human immune cells. Nature Communications, 2017, 8: 1109,
  13. In-vitro cytotoxicity of zinc oxide, graphene oxide, and calcium carbonate nano particulates reinforced high-density polyethylene composite. J. Mater Res. Technol. 2022. 18: 921
  14. Graphene-Doped Polymethyl Methacrylate (PMMA) as a New Restorative Material in Implant-Prosthetics: In Vitro Analysis of Resistance to Mechanical FatigueJ. Clin. Med. 2023, 12, 1269
  15. High performance of polysulfone/ Graphene oxide- silver nanocomposites with excellent antibacterial capability for medical applications. Matter today commun. 2021. 27
  16. Hazard assessment of abraded thermoplastic composites reinforced with reduced graphene oxide. J. Hazard Mater. 2022. 435. 129053
  17. https://www.empa.ch/web/s604/graphene-dust
  18. https://www.graphene-info.com/researchers-asses-health-hazards-graphene-enhanced-composites

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

Graphene: The next revolution in biomedical applications

Graphene:

The next revolution in biomedical applications

Part I. Tissue Engineering

Advances in medicine have reached levels unimagined until recently. Among them, tissue engineering has an important participation. With it is possible to combine cells, biomaterials and biologically active molecules with the aim of repairing or replicating tissues or organs with a function similar to that of the original structure. In principle, biomaterials are used as molecular scaffolds to act as a three-dimensional (3D) support or guide for the anchoring and growth of the cells that will be in charge of forming the new tissue.

The first molecular scaffolds were designed with natural materials such as collagen, glycosaminoglycans (GAGs), chitosan, and alginates; then with artificial compounds such as polylactic acid (PLA), polyglycolic acid (PGA), poly(lactic-co-glycolic) acid (PLGA), polyurethanes (PUs), polytetrafluoroethylene (PTFE), polyethyleneterephthalate (PET); bioceramics such as hydroxyapatite (HA) and tricalcium phosphate; metals such as stainless steel, chrome-cobalt alloys (Co-Cr) or titanium alloys (Ti) and recently, new research is oriented towards the use of nanotechnology.

The relationship between nanotechnology and tissue engineering is due to the fact, that the extracellular matrix (ECM) that helps cells unite and communicate with each other, is made up of a network of nanometer-sized fibers made up of bioactive molecules. It is at this point where nanotechnology opens new possibilities for regenerative medicine, since it has been proven that the use of materials that act on the same nanometric scale as the ECM favors mimicking the physiological environment of the organism to stimulate cell growth and differentiation in a more natural environment.

Among the most studied nanomaterials in recent years are graphene materials, which consist of nanometric sheets of carbon atoms organized in two-dimensional (2D) hexagonal networks. Among the most interesting properties for tissue engineering are: its large surface area, mechanical resistance, thermal conductivity, biocompatibility and finally, an extraordinary ability to share its properties with other materials to improve their original characteristics.

For example, the use of graphene materials within the 3D architecture of certain biopolymers in tests carried out on heart, liver, bone, cartilage, and skin tissues has shown substantial improvements in their physicochemical, mechanical, electrical and biological properties, achieving excellent response. for stem cell adhesion and differentiation.

In 2022, the Andaltec technology center (Spain) reported the development of a material from polymers derived from graphene by 3D printing with great potential for the regeneration of muscle tissue. They demonstrated that in the presence of graphene derivatives, cells contract and expand without an external stimulus, therefore, it has great potential for use in regenerative medicine.

On the other hand, the Division of Postgraduate Studies and Research (DEPeI) on Odontology, UNAM and the National School of Higher Studies (ENES) León Unit, Mx., through a study published in J Oral Res 2021 supports the possibilities of graphene oxide (GO) in the design of biomaterials for dental use. The results of the research carried out with Graphenemex® GO samples, concluded that this nanomaterial in combination with polymethylmethacrylate (PMMA), in addition to improving its physical-mechanical properties, also demonstrated good compatibility and an interesting stimulation of cell proliferation when being evaluated on cultures with gingival-fibroblasts, dental-pulp-cells and human osteoblasts.

In 2020, researchers from the University of Malaga (Spain) published another study that identified GO as the ideal material for regenerative medicine. The study carried out on an animal model, showed high biocompatibility of different types of graphene oxide with dopaminergic cells, favoring their maturation and protecting them from the toxic conditions of Parkinson’s disease. These results postulate GO as an adequate scaffold to test new drugs or develop constructs for cell replacement therapy of Parkinson’s disease.

Despite the large amount of research on the interactions of graphene materials with biological media, there is still a long way to go to have these biomaterials available and in clinical operation. Energeia- Graphenemex, the pioneering Mexican company in Latin America in the research and development of applications with graphene materials, in collaboration with other companies and research centers, seeks to contribute with science to understand these interactions in a security framework, to lay solid foundations on the use of graphene nanotechnology in the biomedical sector for the benefit of society.

Drafting: EF/DHS

References

  1. Graphene and its derivatives: understanding the main chemical and medicinal chemistry roles for biomedical applications. J Nanostructure Chem, 2022, 12:693
  2. Biological and physico-mechanical properties of poly (methyl methacrylate) enriched with graphene oxide as a potential biomaterial. J Oral Res 2021; 10(2):1
  3. Graphene-Based Antimicrobial Biomedical Surfaces. ChemPhysChem 2021, 22, 250
  4. Functionalized Graphene Nanoparticles Induce Human Mesenchymal Stem Cells to Express Distinct Extracellular Matrix Proteins Mediating Osteogenesis. Int J Nanomed 2020:15 2501
  5. Graphene Oxide and Reduced Derivatives, as Powder or Film Scaffolds, Differentially Promote Dopaminergic Neuron Differentiation and Survival. Front. Neurosci., 21 December 2020. Sec. Neuropharmacology Volume 14
  6. International Journal of Nanomedicine 2019:14 5753
  7. Biocompatibility Considerations in the Design of Graphene Biomedical Materials. Adv. Mat. Interfaces 2019, 6, 1900229
  8. Graphene based scaffolds on bone tissue engineering. Bioengineered, 2018, 9:1, 38
  9. When stem cells meet graphene: Opportunities and challenges in regenerative medicine. Biomaterials, 2018, 155, 236
  10. Graphene-based materials for tissue engineering. Adv. Drug Deliv. Rev. 2016,105, 255

Chapter 92 e: Tissue Engineering, Anthony Atala. 2023 McGraw Hill.

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

Graphene as a sustainable alternative for water purification

Graphene as a sustainable alternative

for water purification

Graphene materials, that is, Graphene, Graphene Oxide (GO) and Reduced Graphene Oxide (rGO), are carbon nanostructures that, thanks to their size, area, and surface chemistry, allow the design o new three-dimensional and multifunctional materials with high probabilities. to solve the problems associated with water scarcity.

For example, they are potential coagulant/flocculating agents, this is because they have a large surface area along which there are multiple anchor points capable of capturing a large amount of organic and inorganic matter, that is, they are highly useful for the capture of contaminants.

Main strategies for the use of graphene materials for the capture of contaminants.
  Taken from Environ. Sci. Technol., 2012, 46, 7717.

They are also chemically inert and by being immobilized in a substrate they prevent organic matter from adhering to surfaces. This property, when implemented in membrane technology, would allow a flow of water almost without friction, in other words, the use of graphene materials could make the flow of water remain constant for longer and therefore provide greater energy efficiency.

Likewise, their nanometric size, the arrangement of their sheets and the presence of millions of nanochannels between them make them highly impermeable, acting as a filter for molecules or contaminants.

Ion and water transport through graphene nanochannels.
Taken from J. Phys. Chem. C 2020, 124, 31, 17320.

Finally, the important antimicrobial and photocatalytic properties of graphene and its derivatives, in addition to reducing the microbial load by taking advantage of sunlight, would also help to reduce the requirements for biocidal agents.

Schematic representation of graphene in 3D structures for water purification.
Taken from Gels 2022, 8, 622.

The identification, understanding and use of the properties of graphene for the development of real products has not been an easy task. However, on November 3, 2022, the Graphene flagship, the multidisciplinary project in which almost 10 years ago the European Commission invested 1,000 million euros for Graphene research, announced the results of the Graphil Project, which consisted of the development of a new polysulfone filter with Graphene Oxide that acts as a more efficient mechanical network to trap polluting particles such as heavy metals, antibiotics, viruses, bacteria, toxins, etc., while allowing the passage of clean and safe water.

For its part, Energeia-Graphenemex®, the pioneering Mexican company in Latin America in the research and development of applications with graphene materials, in collaboration with other companies and research centers, joins this search for strategies to improve the availability and quality of water through the use of graphene, hoping in the short term to have all these benefits available to society.

References:

  1. Yu Z, Wei L, Lu L, Shen Y, Zhang Y, Wang J, Tan X. Structural Manipulation of 3D Graphene-Based Macrostructures for Water Purification. Gels. 2022, 29; 8(10):622.
  2. Alessandro Kovtun, Antonio Bianchi, Massimo Zambianchi, Cristian Bettini, Franco Corticelli Giampiero Ruani, Letizia Bocchi,Francesco Stante,Massimo Gazzano, Tainah Dorina Marforio, Matteo Calvaresi, Matteo Minelli,Maria Luisa Navacchia, Vincenzo Palermo and Manuela Melucci. Core–shell graphene oxide– polymer hollow fibers as water filters with enhanced performance and selectivity. Faraday Discuss., 2021, 227, 274.
  3. Sebastiano Mantovani,Sara Khaliha, Laura Favaretto, Cristian Bettini,Antonio Bianchi, Alessandro Kovtun, Massimo Zambianchi, Massimo Gazzano,  Barbara Casentini, Vincenzo Palermo and Manuela Melucci. Scalable synthesis and purification of functionalized graphene nanosheets for water remediation. Chem. Commun., 2021, 57, 3765
  4. Sara Khaliha, Tainah D. Marforio, Alessandro Kovtun, Sebastiano Mantovani, Antonio Bianchi, Maria Luisa Navacchia, Massimo Zambianchi, Letizia Bocchi. Nicoals Boulanger. Artem Iakunkov, Matteo Calvaresi, Alexandr V. Talyzin, Vincenzo Palermo, Manuela Melucci. Defective graphene nanosheets for drinking water purification: Adsorption mechanism, performance, and recovery. FlatChem., 2021, 29 100283.
  5. Yunzhen Zhao, Decai Huang, Jiaye Su, and Shiwu Gao. Coupled Transport of Water and Ions through Graphene Nanochannels. J. Phys. Chem. C 2020, 124, 31, 17320
  6. F. Guo, G. Silverberg, S. Bowers, S.-P. Kim, D. Datta, V. Shenoy and R. H. Hurt, Environmental Applications of Graphene-Based Nanomaterials. Environ. Sci. Technol., 2012, 46, 7717
  7. https://graphene-flagship.eu/graphene/news/graphene-applications-graphil/

Graphene-reinforced lime paints: the revolution in the construction industry

Graphene-reinforced lime paints:

the revolution in the construction industry

Although the exact date on which lime was discovered by man is not known, there are records dating back more than 14,000 years regarding its use. In the case of Mexico, it has been used since pre-Hispanic times both for construction and for nixtamalization, in ancient Greece it was used to color numerous frescoes (2800 B.C.- 1000 A.D.), the Chinese wall was built after stabilizing the soil with lime (500 AD) and among many other historical data, lime became popular in Europe during the Middle Ages for its disinfectant, breathable and fire-retardant properties, being used mainly as a coating on the exterior of houses and barracks. Subsequently, its implementation in the cities extended until the beginning of 1900 and it was not until the middle of that same century that it reached rural areas, a period in which synthetic paints gained ground over lime thanks to their ease of application, wide range of colors and low cost.

However, at the end of the 1970s and due to the awareness of the dangers of some synthetic paints with respect to health and the environmental pollution caused by certain components (heavy metals and volatile organic compounds [VOC]), lime paints once again had a boom as they are safer products and have a smaller footprint on the environment.

Among the benefits of lime-based paints or coatings are that they are 100% natural, ecological and VOC-free products, which absorb CO2 during their hardening process, which means that their use contributes to air purification. They are also breathable materials, that is, they allow the structures to “breathe” and do not concentrate moisture. In addition, they are thermoregulators, this means that they do not allow drastic changes in temperature in the buildings and, on the contrary, they help the buildings to stay cool.

However, and despite their great advantages, one of the main drawbacks of lime-based paints is their high permeability and, therefore, poor resistance to humidity, which is in turn related to limited adherence that requires constant repair work. maintenance. On the other hand, and although antimicrobial or biocidal properties are attributed to lime, it is not convenient to ensure that all the products that contain it offer this protection, since they are materials susceptible to being attacked by microbial species such as Aspergillus spp., Cladosporium spp, Fusarium spp., Trichoderma spp., Actinobacteria and Bacteroidetes among other species responsible for its biodeterioration as well as some infections.

With the aim of contributing to a sustainable present and future, in 2022 the strategic alliance between the companies Energeia-Graphenemex® and Oxical®, after almost 2 years of research, launched a new coating made from modified high-purity lime with Graphene nanoparticles, under the Graphenecal® brand.

Graphenecal nanoengineering reaches the market to create a new generation of lime-based coatings that exceed the characteristics of water-based paints made from chemical resins. The nanometric network that generates the graphene nanoparticles in combination with the high-purity lime and other natural products used in its formulation, compacts and organizes its entire structure at the molecular level, offering greater durability to the coating and improving its characteristics, thanks to the perfect balance that exists between greater impermeability (>50-80%) with adequate breathability avoiding the accumulation of moisture on surfaces, coupled with the excellent benefits offered by its great antimicrobial capacity (>99.9%) that prevents the adhesion and formation of microbial biofilms not only to protect against the biodeterioration of structures but also as a tool in infection control, among other advantages such as excellent adhesion, covering power, resistance against the effects of weather, greater thermoregulation, CO2 capture and lower carbon footprint in comparison with other products, no need for chemical additives, biocide products or contaminants, placing Mexico at the vangard in the development of environmentally friendly products.

Greater Impermeability

After 4 days of application, Graphenecal is 50% more waterproof than lime-based paints without graphene. As of day 30, this property rises to 85% without affecting the breathability of the product.
Representative image of the impermeability of Graphenecal on two different substrates.

Antimicrobial Capacity

On the graphene-free lime paint, a microbial biofilm was formed on more than 90% of its surface. The Graphenecal coated area remained free of contamination during the test.

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.