Influence of Ionic Liquids on the Aggregation and Preaggregation Phenomena of Asphaltenes in Model Solvent Mixtures by Molecular Dynamics Simulations and Quantum Mechanical Calculations: The Effect of Cation’s Shape and Size Rafaela N. Martins, Lucas G. Celia-Silva, João P. Prates Ramalho, Pedro Morgado, Eduardo J. M. Filipe, Luís F. G. Martins Energy and Fuels, 2024 The merits of ionic liquids (ILs) as additives to influence the solid–liquid behavior of asphaltenes in crude oil models have been well-established in specialized literature. The direct interaction between ionic liquids and asphaltenes is recognized as a key factor for the role played by these additives in the asphaltene aggregation process, which depends on the structural details of the ionic liquids used (and also on the model considered for the asphaltenes). In a previous paper, we presented a systematic molecular dynamics study of the effect of 1-alkyl-3-methyl imidazolium-based ionic liquids on the asphaltene preaggregation phenomenon, focusing on the effect of the alkyl chain length of the cation and on the size of the anion. In this work, this study is extended to evaluate the effect of the shape and size of the cation head. The preaggregation phenomena in toluene/n-heptane mixtures and the asphaltene/IL interactions are studied here by molecular dynamics simulations and density functional theory (DFT) calculations, using N-alkylpyridinium, N-alkyl isoquinolinium, and 1-alkyl-3-methyl benzimidazolium chloride ILs, with alkyl chains containing between 4 and 10 carbon atoms as additives. These additives show a general dispersing effect in n-heptane-rich systems, with the N-alkyl isoquinolinium-based ILs with longer alkyl chains (especially C8 but also C10) being the most active ones. The asphaltene/IL interaction is found to be enhanced by cations with two condensed aromatic rings instead of one, which seems to highlight the importance of the π–π stacking contact. However, the most interactive family of ILs (1-alkyl-3-methyl benzimidazolium chloride) is also the one that induces asphaltene aggregation, especially for shorter alkyl side chains (with 33% larger aggregates than the systems without additive for mixtures with equal proportions of the two solvents), probably representing a binder effect for asphaltenes. Although by molecular simulation, the N-alkyl isoquinolium-based ILs showed the clearest dispersing effect toward asphaltenes and the most intense interactions with them, they also presented the lowest interaction energies of the asphaltene–IL dimers obtained by DFT, and this was found to be the consequence of a specific cation–anion interaction only for this family of ILs, which is close to a covalent bond. This work is a valuable addition to the understanding of the molecular interactions that govern asphaltene aggregation in the presence of additives, and contributes to the selection and design of better additives to prevent or induce asphaltene aggregation in crude oil.
Encapsulation of Nanoparticles as Corrosion Inhibitors for Smart Coatings Luana B. Furtado, Carolina Garín Correa, Rafaela C. Nascimento Encapsulated Corrosion Inhibitors for Eco Benign Smart Coatings, 2024 Encapsulating corrosion inhibitors inside nanostructures prevents and repairs corrosion damage over a metallic surface while augmenting the barrier properties of smart coatings. Nanoreservoirs are composed mainly of organic or inorganic containers, but in some cases, a hybrid matrix. The design of this structure depends on the nature of the active species that inhibit corrosion and its interaction with the nanocontainer. The controlled release of the active species helps maintain the steady and continuous performance of the coating. The design strategies, nature of the nanoparticles and the active species applied to smart coatings are explored in this chapter. The mechanism of the inhibition systems is usually pH dependent, whereby the surroundings of damaged areas stimulate the release of active species that lead to a self-healing process. The controlled release of inhibitors and the desired barrier properties of coatings can be improved since the evaluation of these systems seems to be mostly qualitative. Thus, more quantitative tests would help to compare results and guide future design strategies. As encapsulating agents, these nanoparticles might respond to salinity, pH gradient, species concentration and temperature, and should be addressed in future research.
Modified Biopolymers and Their Wastes as Corrosion Inhibitors Luana Barros Furtado, Rafaela C. Nascimento, Carolina Garín Correa, Camila Dias dos Reis Barros Biomass Wastes for Sustainable Industrial Applications A Waste to Wealth Approach, 2024 Biopolymers are an ascending category of green corrosion inhibitors. They are natural polymers produced by plants or animals, polysaccharides being the most widely used corrosion inhibitors. The chemical functionalization of biopolymers alters their physicochemical properties, which can improve their inhibitory activity and efficiency. Introducing more adsorption sites on the metallic surface increases its inhibitory activity. These inhibitors are classified based on their application and studied at specific concentration ranges that differ from those of traditional synthetic compounds. Strategic selection of the modifying agent aims to improve active adsorption sites and biopolymer solubility through enhanced functionalization. In this respect, computational studies help by providing the chemical descriptors that support this focused selection of the modifying agent. Several reports have demonstrated that functionalization increases inhibition potential compared to the original biopolymer. However, attention should be paid to the synthesis costs versus the improved efficiency provided by chemical modification, as well as homopolymer and/or modifying agent removal, in addition to the solubility and steric effects that can result from certain types of functionalization. Most of the published literature revealed an increase in efficiency with inhibitor concentration and a decrease in performance with rising temperature. Significant improvement is needed to achieve competitive performance that allows the industrial application of biopolymers as corrosion inhibitors.
Biopolymers as corrosion inhibitors: Relative inhibition potential of biopolymers and grafted biopolymers Rafaela C. Nascimento, Luana Barros Furtado, Maria José O. C. Guimarães Grafted Biopolymers as Corrosion Inhibitors Safety Sustainability and Efficiency, 2023 Biopolymers are macromolecular structures produced by plant or animal cells that can be copolymerized to form grafted biopolymers, thus enhancing their properties. The most common biopolymers used as corrosion inhibitors are polysaccharides such as starch, cellulose derivatives, chitosan, dextrin, pectin, and guar gum, among others. A strategy to produce new biopolymers involves the chemical modification of functional groups (hydroxyl, carboxylic acid, and amino groups) naturally present in the macromolecular structure of polysaccharides. Understanding their performance as corrosion inhibitors should address some of the factors that affect inhibition efficiency. The most widely studied corrosive media are HCl, H 2 SO 4, and NaCl. Inhibitors are evaluated mostly in concentrations ranging from 25–2000ppm, and from 303–338K, where most of the literature reports an increase in efficiency with inhibitor concentration. Grafting aims at improving inhibition efficiency due to oxygen and nitrogen in the co-monomer structure.
Experimental and Theoretical Studies of Tailor-made Schiff Bases as Corrosion Inhibitors for Carbon Steel in HCl Luana B. Furtado, Gabriel B. Leoni, R. C. Nascimento, Pedro Henrique C. Santos, Fábio J. F. S. Henrique, Maria José O. C. Guimarães, Simone L. D. C. Brasil Materials Research, 2023 Strong acids used in industrial applications as cleaning, descaling, among others, can severely damage metallic structures, requiring corrosion inhibitors to diminish or avoid these issues. Since many conventional compounds used for this purpose may result in environmental and human health issues, eco-friendly compounds such as Schiff bases have been recently investigated. The synthesis of three novel Schiff bases (SBs) was confirmed by infrared spectroscopy (FTIR) and hydrogen nuclear magnetic resonance (1H-NMR). Weight loss measurements were carried out in 1 M HCl over 303K-333K. Furthermore, the combination of these compounds with a surfactant improved the efficiencies, reaching an efficiency of 93%. Optical and scanning electron microscopies confirmed the reduced roughness and pit depths of carbon steel samples. Density-functional theory calculations for neutral forms of SBs revealed that the geometrical and the energetical parameters are similar for the three studied SBs. The geometrical results exhibited more planar structures of protonated species, improving the chemical and physical interactions between aromatic rings and metallic atoms.
Influence of Ionic Liquids on the Aggregation and Pre-aggregation Phenomena of Asphaltenes in Model Solvent Mixtures by Molecular Dynamics Simulations and Quantum Mechanical Calculations Lucas G. Celia-Silva, Rafaela N. Martins, Alfredo J. Palace Carvalho, João P. Prates Ramalho, Pedro Morgado, Eduardo J.M. Filipe, Luís F.G. Martins Energy and Fuels, 2022 This work presents a systematic study of asphaltene pre-aggregation phenomena in the absence and in the presence of ionic liquids (ILs) from the family of 1-alkyl-3-methylimidazolium by molecular dynamics simulations. The effects of the alkyl chain length of the cation (studying ILs with alkyl chains between C4 and C10) and of the dimension of the anion (testing chloride and bromide) on the aggregation behavior of asphaltenes have been studied. To correlate the results obtained with the direct interaction between each additive and asphaltene, the latter was investigated both by the analysis of the radial distribution functions obtained by molecular dynamics simulations and quantum mechanical calculations. The DFT method was used to calculate the relative stability of the asphaltene-ionic liquid dimers and also the energy, shape, and spatial distribution of frontier orbitals. It was found that all the ionic liquids studied present a dispersing effect on asphaltene in model solvents, except for mixtures rich in toluene where, in most cases, the opposite effect is observed. This is accompanied by the interaction intensity as measured by radial distribution functions. The effects of the alkyl side chain length of the cation and of the anion radius are subtler, but it seems that the asphaltene dispersion effect increases with the length of the cation’s alkyl side chain and decreases with the radius of the anion; these effects are more clearly observed in the mixtures richer in n-heptane. These trends were corroborated by DFT calculations, which showed that the energetic stability of the asphaltene-additive dimer is as higher as the alkyl chain is longer and the anion is smaller. Pre-aggregation phenomena were also studied in mixtures containing CO2, which proved to be a precipitating agent as observed experimentally. The relative performances of the IL studied were not altered by the presence of CO2.
Evaluation of a novel Schiff Base as greener corrosion inhibitor for API P110 carbon steel in acidizing fluids 21st International Corrosion Congress Icc Intercorr Wco 2021, 2021
On the diffusion of carbamazepine, acetaminophen and atenolol in water: An experimental and theoretical approach FS Mendes, ADA Goncalves, FIS Guiomar, RN Martins, JPP Ramalho, ... Fluid Phase Equilibria 580, 114056 , 2024 2024 Citations: 7
Influence of Ionic Liquids on the Aggregation and Preaggregation Phenomena of Asphaltenes in Model Solvent Mixtures by Molecular Dynamics Simulations and Quantum Mechanical … RN Martins, LG Celia-Silva, JPP Ramalho, P Morgado, EJM Filipe, ... Energy & Fuels 38 (5), 3693-3712 , 2024 2024 Citations: 3
Biopolymers as corrosion inhibitors: relative inhibition potential of biopolymers and grafted biopolymers RC Nascimento, LB Furtado, MJOC Guimarães Grafted biopolymers as corrosion inhibitors: safety, sustainability, and … , 2023 2023 Citations: 11
Experimental and theoretical studies of tailor-made schiff bases as corrosion inhibitors for carbon steel in HCl LB Furtado, GB Leoni, RC Nascimento, PHC Santos, FJFS Henrique, ... Materials Research 26, e20220398 , 2023 2023 Citations: 11
On the diffusion of ketoprofen and ibuprofen in water: An experimental and theoretical approach FS Mendes, CEM Cruz, RN Martins, JPP Ramalho, LFG Martins The Journal of Chemical Thermodynamics 178, 106955 , 2023 2023 Citations: 13
Influence of ionic liquids on the aggregation and pre-aggregation phenomena of asphaltenes in model solvent mixtures by molecular dynamics simulations and quantum mechanical … LG Celia-Silva, RN Martins, AJP Carvalho, JPP Ramalho, P Morgado, ... Energy & Fuels 36 (16), 9048-9065 , 2022 2022 Citations: 11
LÍQUIDOS IÔNICOS COM APLICAÇÃO NA CAPTURA DE CARBONO: MODELAÇÃO E SIMULAÇÃO RN Martins, VCGM Ferrari, LFG Martins Revista Univap 28 (58) , 2022 2022
Effects of temperature, concentration and synergism on green Schiff bases synthesized from vanillin in applications as corrosion inhibitors for carbon steel in well stimulation LB Furtado, RC Nascimento, FJFS Henrique, MJOC Guimaraes, ... Journal of Petroleum Science and Engineering 213, 110401 , 2022 2022 Citations: 30
Green eugenol oligomers as corrosion inhibitors for carbon steel in 1M HCl LB Furtado, RC Nascimento, MJOC Guimarães, SLDC Brasil, SHR Barra Materials Research 25, e20220012 , 2022 2022 Citations: 5
Cleaner corrosion inhibitors using Peumus boldus Molina formulations in oil well acidizing fluids: gravimetric, electrochemical and DFT studies LB Furtado, RC Nascimento, MJOC Guimaraes, FJFS Henrique, ... Sustainable Chemistry and Pharmacy 19, 100353 , 2021 2021 Citations: 19
Sustainable corrosion inhibitors II: synthesis, design, and practical applications CM Hussain, C Verma (No Title) , 2021 2021 Citations: 8
Plant extracts as green corrosion inhibitors LB Furtado, R Nascimento Sustainable corrosion inhibitors II: synthesis, design, and practical … , 2021 2021 Citations: 7
Evaluation of a novel Schiff Base as greener corrosion inhibitor for API P110 carbon steel in acidizing fluids LB Furtado, RC Nascimento, J Rocha, PR Seidl, JACP Gomes, ... 2021
Storage time evaluation of a residue from wine industry as a microencapsulated corrosion inhibitor for 1 M HCl LB Furtado, JC Rocha, JACP Gomes, RC Nascimento, PR Seidl, ... Materials Chemistry and Physics 256, 123739 , 2020 2020 Citations: 19
Eco-friendly corrosion inhibitors based on Cashew nut shell liquid (CNSL) for acidizing fluids LB Furtado, RC Nascimento, PR Seidl, MJOC Guimarães, LM Costa, ... Journal of Molecular Liquids 284, 393-404 , 2019 2019 Citations: 79
Synergistic effect of propargyl alcohol, octadecylamine, and 1, 3-dibutyl thiourea for API P110 alloys in acetic and formic acidic solutions used in oil well acidizing RC Nascimento, LB Furtado, MJOC Guimarães, PR Seidl, JC Rocha, ... Journal of Molecular Liquids 256, 548-557 , 2018 2018 Citations: 25
Formulações inibidoras verdes de compostos fenólicos para fluidos inorgânicos de acidificação LB Furtado, RC Nascimento, MJOC Guimarães, PR Seidl 2016
Study of biofuels corrosiveness; Estudo da corrosividade de biocombustiveis RC Nascimento, LPN Branco, MJOC Guimaraes, PR Seidl 2012
Rafaela C. Nascimento, Lucas PN Branco b, Camilla FS Moura b MJOC Guimarães, PR Seidl 2012
Preparação e formulação de bases saponáceas oriundas de óleos vegetais reciclados GSL Magalhães, RC Nascimento TCC (Graduação)-Curso de Química Industrial, Universidade Federal do Rio de … , 2009 2009 Citations: 1
MOST CITED SCHOLAR PUBLICATIONS
Eco-friendly corrosion inhibitors based on Cashew nut shell liquid (CNSL) for acidizing fluids LB Furtado, RC Nascimento, PR Seidl, MJOC Guimarães, LM Costa, ... Journal of Molecular Liquids 284, 393-404 , 2019 2019 Citations: 79
Effects of temperature, concentration and synergism on green Schiff bases synthesized from vanillin in applications as corrosion inhibitors for carbon steel in well stimulation LB Furtado, RC Nascimento, FJFS Henrique, MJOC Guimaraes, ... Journal of Petroleum Science and Engineering 213, 110401 , 2022 2022 Citations: 30
Synergistic effect of propargyl alcohol, octadecylamine, and 1, 3-dibutyl thiourea for API P110 alloys in acetic and formic acidic solutions used in oil well acidizing RC Nascimento, LB Furtado, MJOC Guimarães, PR Seidl, JC Rocha, ... Journal of Molecular Liquids 256, 548-557 , 2018 2018 Citations: 25
Cleaner corrosion inhibitors using Peumus boldus Molina formulations in oil well acidizing fluids: gravimetric, electrochemical and DFT studies LB Furtado, RC Nascimento, MJOC Guimaraes, FJFS Henrique, ... Sustainable Chemistry and Pharmacy 19, 100353 , 2021 2021 Citations: 19
Storage time evaluation of a residue from wine industry as a microencapsulated corrosion inhibitor for 1 M HCl LB Furtado, JC Rocha, JACP Gomes, RC Nascimento, PR Seidl, ... Materials Chemistry and Physics 256, 123739 , 2020 2020 Citations: 19
On the diffusion of ketoprofen and ibuprofen in water: An experimental and theoretical approach FS Mendes, CEM Cruz, RN Martins, JPP Ramalho, LFG Martins The Journal of Chemical Thermodynamics 178, 106955 , 2023 2023 Citations: 13
Biopolymers as corrosion inhibitors: relative inhibition potential of biopolymers and grafted biopolymers RC Nascimento, LB Furtado, MJOC Guimarães Grafted biopolymers as corrosion inhibitors: safety, sustainability, and … , 2023 2023 Citations: 11
Experimental and theoretical studies of tailor-made schiff bases as corrosion inhibitors for carbon steel in HCl LB Furtado, GB Leoni, RC Nascimento, PHC Santos, FJFS Henrique, ... Materials Research 26, e20220398 , 2023 2023 Citations: 11
Influence of ionic liquids on the aggregation and pre-aggregation phenomena of asphaltenes in model solvent mixtures by molecular dynamics simulations and quantum mechanical … LG Celia-Silva, RN Martins, AJP Carvalho, JPP Ramalho, P Morgado, ... Energy & Fuels 36 (16), 9048-9065 , 2022 2022 Citations: 11
Sustainable corrosion inhibitors II: synthesis, design, and practical applications CM Hussain, C Verma (No Title) , 2021 2021 Citations: 8
On the diffusion of carbamazepine, acetaminophen and atenolol in water: An experimental and theoretical approach FS Mendes, ADA Goncalves, FIS Guiomar, RN Martins, JPP Ramalho, ... Fluid Phase Equilibria 580, 114056 , 2024 2024 Citations: 7
Plant extracts as green corrosion inhibitors LB Furtado, R Nascimento Sustainable corrosion inhibitors II: synthesis, design, and practical … , 2021 2021 Citations: 7
Green eugenol oligomers as corrosion inhibitors for carbon steel in 1M HCl LB Furtado, RC Nascimento, MJOC Guimarães, SLDC Brasil, SHR Barra Materials Research 25, e20220012 , 2022 2022 Citations: 5
Influence of Ionic Liquids on the Aggregation and Preaggregation Phenomena of Asphaltenes in Model Solvent Mixtures by Molecular Dynamics Simulations and Quantum Mechanical … RN Martins, LG Celia-Silva, JPP Ramalho, P Morgado, EJM Filipe, ... Energy & Fuels 38 (5), 3693-3712 , 2024 2024 Citations: 3
Preparação e formulação de bases saponáceas oriundas de óleos vegetais reciclados GSL Magalhães, RC Nascimento TCC (Graduação)-Curso de Química Industrial, Universidade Federal do Rio de … , 2009 2009 Citations: 1
LÍQUIDOS IÔNICOS COM APLICAÇÃO NA CAPTURA DE CARBONO: MODELAÇÃO E SIMULAÇÃO RN Martins, VCGM Ferrari, LFG Martins Revista Univap 28 (58) , 2022 2022
Evaluation of a novel Schiff Base as greener corrosion inhibitor for API P110 carbon steel in acidizing fluids LB Furtado, RC Nascimento, J Rocha, PR Seidl, JACP Gomes, ... 2021
Formulações inibidoras verdes de compostos fenólicos para fluidos inorgânicos de acidificação LB Furtado, RC Nascimento, MJOC Guimarães, PR Seidl 2016
Study of biofuels corrosiveness; Estudo da corrosividade de biocombustiveis RC Nascimento, LPN Branco, MJOC Guimaraes, PR Seidl 2012
Rafaela C. Nascimento, Lucas PN Branco b, Camilla FS Moura b MJOC Guimarães, PR Seidl 2012
