Mono‐, Di‐ and Tetra‐Cationic Surfactants as Carbon Steel Corrosion Inhibitors

Corrosion inhibition of three new synthesized cationic surfactants, N‐(2‐(((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)amino)ethyl)‐N‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)dodecan‐1‐aminium bromide I(4N), N¹,N²‐didodecyl‐N¹‐((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)‐N²‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)ethane‐1,2‐diaminium bromide II(4N) and 1‐dodecyl‐4‐((E)‐((2‐(dodecyl(2‐(dodecyl((Z)‐4‐(1‐dodecylpyridin‐1‐ium‐4‐yl)but‐3‐en‐1‐yl)ammonio)ethyl)ammonio)ethyl)imino)methyl)pyridin‐1‐ium bromide IV(4N) on carbon steel was investigated by weight loss, electrochemical impedance spectroscopy and polarization measurements. Results show that the synthesized cationic surfactants inhibit corrosion of carbon steel in 1 M HCl. The inhibitive action occurs by virtue of adsorption on the metal surface following a Langmuir adsorption isotherm model. Polarization curves reveal that the investigated cationic surfactants can be classified as mixed inhibitor types. The variations in the corrosion inhibition efficiency between three cationic surfactants are correlated with their chemical structures, with more hydrophobic surfactants yielding higher inhibition efficiency.     

Effects of structure of the ionic head of cationic surfactant on its inhibition of acid corrosion of mild steel

Two n-alkyl-quaternary ammonium compounds were studied as corrosion inhibitors for acid corrosion of mild steel using electrochemical and weight loss methods. The two compounds are hexadecylpyridinium bromide (HDPB) and hexadecyltrimethyl ammonium bromide (HDTB). The influence of the structure of the ionic head on the inhibition action of the two cationic surfactants was studied by analyzing the data at different concentrations and temperatures. The inhibition efficiency increases with the concentration. It increases with temperature in the case of HDPB but decreases in the case of HDTB. The apparent activation energy, E _a of corrosion in the presence of HDPB was found to be lower than in blank (0.5 m H₂SO₄). In the case of HDTB, E _a was larger than that of the blank. A larger extent of adsorption for HDPB on the metal surface was evident from the larger negative values of the free energy of adsorption. The results yielded the extent and mode of adsorption of the inhibitors on mild steel. The stronger adsorption of HDPB was attributed to the differences in the molecular structures of the inhibitors.     

Comparison of a Cationic Gemini Surfactant and the Corresponding Monomeric Surfactant for Corrosion Protection of Mild Steel in Hydrochloric Acid

A cationic gemini surfactant, N,N′-didodecyl-N,N,N′,N′-tetramethyl-1,4-butanediammonium dibromide (12-4-12) and the corresponding monomeric surfactant dodecyltrimethylammonium bromide were compared with respect to corrosion inhibition efficiency in 1 M hydrochloric acid solution. Polarization and electrochemical impedance spectroscopy were used to evaluate corrosion inhibition. The 12-4-12 surfactant showed an extremely high corrosion inhibition efficiency at very low concentration. Surface tension measurements performed under the strongly acidic conditions revealed that the gemini surfactant is remarkably electrolyte tolerant, which is beneficial for adsorption at the steel surface.     

Study on the dyeing properties of hemicyanine dyes. II. Cationic dyeable polyester

The absorption spectra of two hemicyanine fluorescent dyes, namely, trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐ethyl pyridinium bromide (DHEASPBr‐C₂) and trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐octyl pyridinium bromide (DHEASPBr‐C₈), were studied at various levels of pH and high temperatures, and were then employed to dye cationic dyeable polyester. Their dyeing properties, fluorescent reflectance and colorimetric properties were explored. The novel fluorescent dyes existed in two forms of monocation and dication in solutions at low pH and high temperature. Overall, the influence of pH on colour depth and the maximum reflectance of dyed cationic dyeable polyester was extremely small. The adsorption mechanism of DHEASPBr‐C₂ and DHEASPBr‐C₈ on cationic dyeable polyester fibres was in good accord with the Langmuir type. Compared with DHEASPBr‐C₂, DHEASPBr‐C₈ exhibited comparatively faster adsorption rate, higher affinity and dye uptake, while its fluorescence shown by cationic dyeable polyester was slightly weak.     

CO2/N2 Triggered Switchable Surfactants with Imidazole Group

In order to overcome the hydrolysis of 2-alkyl-1-hydroxyethyl imidazoline and its unsatisfactory emulsification–demulsification switchability to water-alkane, the long-chain N-alkylimidazole compounds were synthesized by n-octyl bromide, n-decyl bromide, n-dodecyl bromide, n-tetradecyl bromide and n-hexadecyl bromide with imidazole, respectively and characterized by MS, ¹H NMR and FTIR. The long-chain N-alkylimidazole compounds can be reversibly transformed into charged surfactants by exposure to CO₂. Surface tension values indicated that N-alkylimidazolium bicarbonates had excellent surface activity compared with corresponding conventional surfactants with a lower γ _CMC. The surface behaviors of the five surfactants can be illustrated by A _min. Five conductivity cycles by bubbling CO₂ and N₂ alternately indicated that these surfactants could be switched by CO₂ reversibly and repeatedly. Emulsions were repeatedly stabilized for five cycles by N-alkylimidazolium bicarbonate and broken by bubbling N₂ through the solutions to reverses the reaction, releasing CO₂.     

Inhibition of mild steel corrosion in acidic medium using starch and surfactants additives

The corrosion inhibition of mild steel in 0.1M H₂SO₄ in presence of starch (polysaccharide) was studied using weight loss and potentiodynamic polarization measurements in the temperature range of 30–60°C. Starch inhibits the corrosion rates of mild steel to a considerable extent; the maximum inhibition efficiency (%IE) being 66.21% at 30^oC in presence of starch concentration of 200 ppm. The effect of the addition of very small concentration of sodium dodecyl sulfate and cetyl trimethyl ammonium bromide on the corrosion inhibition behavior of starch was also studied. The IE of starch significantly improved in presence of both the surfactants. The effect of surfactants on the corrosion inhibition behavior of starch appears to be synergistic in nature. Starch alone and in combination with surfactants is found to obey Langmuir adsorption isotherm from the fit of the experimental data of all concentration and temperature studied. Phenomenon of physical adsorption is proposed from the trend of IE with temperature and also the values E_a, ΔG_ads, and Q_ads obtained. The results obtained by potentiodynamic polarization measurements are consistent with the results of the weight loss measurement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Systematic Study of Mixed Surfactant Solutions of a Cationic Ester-Bonded Dimeric Surfactant with Cationic, Anionic and Nonionic Monomeric Surfactants in Aqueous Media

A novel cationic biodegradable dimeric (gemini) surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16), containing an ester-linked spacer was synthesized. Its pure and mixed micellization properties with monomeric surfactants cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl alcohol ethoxylate (20EO) and tert-octylphenol ethoxylate (9.5EO) were investigated by surface tension measurements at 30 °C. The critical micelle concentration (CMC) of 16-E2-16 is well below that of cetyl trimethyl ammonium chloride containing the same number of carbon atoms in the hydrophobic tail per polar head. At different mole fractions of the gemini surfactant, the CMCs of the gemini-conventional binary mixtures were determined and were found to be less than the ideal CMC values in all the cases indicating synergistic interactions. Aggregation number and Stern–Volmer constant, obtained by the fluorescence quenching technique, also support the synergistic behavior of the surfactant systems.     

Mixed Stability and Antimicrobial Properties of Gluconamide-Type Cationic Surfactants

The stability of anionic-cationic surfactant solutions and the antimicrobial properties of novel N,N-dimethyl-N-[3-(gluconamide/lactobionamide)]propyl-N-alkylammonium bromides (CnDGPB and CnDLPB), N-methyl-N-hydroxyethyl group-N-[3-(gluconamide)-propyl]-N-alkylammonium bromide (CnMHGPB) and star-shaped gluconamide-type cationic surfactants N-dodecyl-N,N-bis[(3-d-gluconylamido)propyl]-N-alkylammonium bromide (CnDBGB) were investigated. Mixed stability in combination with sodium n-alkylbenzenesulfonate (LAS) was determined via transmittance; stability is achieved when percent transmittance was greater than 90 %. Transmittance results suggest that these cationic surfactants can form stable solutions with anionic surfactants over a broad concentration range. The inhibition activity of C _n DBGB is the best among the three kinds of glucocationic surfactants. Antimicrobial activity of C₁₂ surfactants was the best, C₁₄ was the second and C₁₀ was the worst. Moreover, antibacterial activity of glucose-based cationic surfactants was greater than lactose-based cationic surfactants.     

Corrosion inhibition of iron in 1 M HCl by some gemini surfactants in the series of alkanediyl-α,ω-bis-(dimethyl tetradecyl ammonium bromide)

Three new gemini surfactants in the series of alkanediyl-α,ω-bis-(dimethylalkyl ammonium bromide) were synthesised and tested as corrosion inhibitors of iron in hydrochloric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the surfactants studied are good cathodic inhibitors and act on the cathodic hydrogen reaction without modifying its mechanism. EIS results show that the changes in the impedance parameters (R_T and C_dl) with concentration of surfactants studied is indicative of the adsorption of molecules of surfactant leading to the formation of a protective layer on the surface of iron. The effect of the temperature on the iron corrosion in both 1 M HCl and 1 M HCl with addition of various concentrations of 1,2-ethane bis-(dimethyl tetradecyl ammonium bromide) in the range of temperature 20–60 °C was studied. The associated apparent activation corrosion energy has been determined.     

Synthesis of Bis[<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-(alkylamideethyl)ethyl] Triethylenediamine Bromide Surfactants and Their Oilfield Application Investigation

Bis[N,N′-(alkylamideethyl)ethyl] triethylenediamine surfactants are quaternary ammonium salt Gemini surfactants with amide, which are synthesized from fatty acid (dodecanoic, hexadecanoic, tetradecanoic and octadecanoic) methyl esters, triethylene tetramine and ethyl bromide. The chemical structures of the prepared compounds were characterized by elemental analysis, FTIR and ¹H-NMR spectra, melting point and Krafft point. Several properties of the synthesized surfactants were studied including surface tension, critical micelle concentration, interfacial tension, emulsification power, salt effect, corrosion inhibition efficiency and biological activity. The results show that the surface activity, critical micelle concentration and interfacial activity are correlated to their chemical structures. The emulsification power measurements of these surfactants show their low emulsifying tendency towards Tazhong’s crude oil from Tarim Oilfield. The synthesized surfactants also exhibit high biocidal activity towards Gram-positive and Gram-negative bacteria and fungi. This activity increases with the increase of alkyl chain length. The corrosion measurement of these surfactants in acidic media with a weight loss technique show good protection of mild steel alloys against acidic environments. These properties suggest that the synthesized compounds have potential for application in the oilfield area.     

Synthesis and Characterization of Cationic Surfactants Based on N‐Hexamethylenetetramine as Active Microfouling Agents

Four cationic surfactants of quaternary hexammonium silane chloride based on hexamethylenetetramine and alkyl chloride were synthesized. The chemical structures of the prepared cationic surfactants were elucidated using Fourier transform infrared (FT‐IR) spectroscopy and mass spectrometry analysis. The surface and thermodynamic properties of the prepared surfactants were also studied. The performance of these cationic surfactants as microfouling agents against two strains of Gram‐negative bacteria, namely, Pseudomonas aeruginosa and Escherichia coli, and two strains of Gram‐positive bacteria, namely, Staphylococcus aureus and Bacillus subtilis, were evaluated as antimicrobial agents. The results showed that the maximum antimicrobial activity was detected for N‐hexamethylenetetramine‐N‐ethyl silane ammonium trichloride (Ah). The maximum and minimum antimicrobial activities were 73 and 60 % against S. aureus and E. coli, respectively, at a concentration of 5 mg/l, pH 7, and 37 °C.     

Poly(acrylamide-chitosan) Hydrogels: Interaction with Surfactants

Semi-interpenetrating hydrogels were prepared from hydrophilic acrylamide and cationic natural biopolymer chitosan, N,N¹-methylenebisacrylamide and water-soluble redox initiating system (ammonium persulfate/N,N,N¹,N¹-tetramethylethylenediamine). The interaction of these hydrogels with different surfactants such as sodiumdodecylsulphate (SDS, anionic), N-cetyl N,N,N-trimethyl ammonium bromide (CTA, cationic) and Tween20 (T20 non-ionic) was studied. The chemical structure of the hydrogels treated with surfactant was characterized by FTIR spectroscopy and the morphology of hydrogels was characterized by scanning electron microscopy (SEM). The thermal properties of surfactant-treated hydrogels were evaluated by TGA analysis.     

Synergistic Behavior of a Triblock Copolymer with Anionic and Cationic Surfactants in Aqueous Solution

The synergistic behavior of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer in aqueous solution with the synthesized anionic surfactants [decyl sulfonate (A10), myristyl sulfonate (A14) and cetyl sulfonate (A16)] and cationic surfactants [decyl pyridinium bromide (C10), myristyl peridinium bromide (C14) and cetyl pyridinium bromide (C16)] was investigated using a surface tension technique at 25 °C. The results show that the CMC values of binary mixtures for anionic and cationic surfactants with the triblock copolymer are lower than that of single surfactants. The synergistic interaction between surfactant molecules and copolymer molecules in binary mixed solution enhance the adsorption of surfactant molecules at the interface. The micellar mole fractions (X _m) and the interaction parameter (β) of these surfactants in mixed micelles were determined.

Effects of surfactants and their mixtures on inhibition of the corrosion process of ferritic stainless steel

The corrosion inhibition characteristics regarding mixtures of cationic/zwitterionic types of surfactant (Myristyltrimethylammonium bromide/Palmitylsulfo-betaineas), and non-ionic surfactant TRITON-X-405 mixed with 1 mM of KBr, as corrosion inhibitors for stainless steel (SS) (type X4Cr13) in aqueous solutions of 2 M H₂SO₄ were investigated using potentiodynamic polarisation measurements. The polarisation data showed that mixtures of the surfactants used in this study acted as mixed-type inhibitors, adsorbing on the stainless steel surface in agreement with the Flory-Huggins adsorption isotherm. The tensiometric results of this study suggest the existence of a second state of aggregation for zwitterionic/cationic surfactant mixtures. From these values of the free energy of adsorption, which in both mixtures decreased with respect to a single surfactant, we concluded that the adsorption in mixtures was stronger. The mixtures studied here showed good inhibition properties for ferritic stainless steel type X4Cr13 in 2 M H₂SO₄ solution.     

Synthesis and Characterization of a Novel Series of Cationic Fumaric Polymerizable Emulsifiers

A series of novel cationic fumaric polymerizable emulsifiers (named as F series emulsifiers) were synthesized. The chemical structures of these emulsifiers were confirmed by ¹H NMR and MS and their minimal inhibitory concentrations to Escherichia coli were determined. Antibacterial tests of latex films showed that [2-(N-benzyl-N,N-dimethylamino)ethyl]dodecyl fumaric ammonium bromide, [2-(N-benzyl-N,N-dimethylamino)ethyl]decyl fumaric ammonium chloride and [2-(N-benzyl-N,N-dimethylamino)ethyl]dodecyl fumaric ammonium chloride can possibly be used as a polymerizable bactericides.     

Surface Properties,Thermodynamic Aspects and Antimicrobial Activity of Some Novel Iminium Surfactants

Novel iminium compounds namely p-benzylidene benzyldodecyl iminium chloride (I), p-benzylidene benzylhexadecyl iminium chloride (II), p-benzylidene benzyloctadecyl iminium chloride (III) were prepared and characterized using FTIR, ¹H-NMR and mass spectroscopy. The surface properties such as surface and interfacial tension, and biological activity of these surfactants were investigated. The surface parameters including critical micelle concentration, maximum surface excess, and minimum surface area. Efficiency and effectiveness were calculated, as well as free energies of micellization and adsorption. The prepared cationic surfactants exhibit a better biological activity than the used reference cetyl trimethyl ammonium bromide.     

The Effects of Amide Bonds and Aromatic Rings on the Surface Properties and Antimicrobial Activity of Cationic Surfactants

The cationic surfactants containing aromatic rings and amide bonds, N,N-dimethyl-N-dodecyl-2-pyrimidinylcarbamoylmethyl ammonium chloride ( a ), N,N-dimethyl-N-dodecyl-2-thiazolylcarbamoylmethyl ammonium chloride ( b ), and N,N-dimethyl-N-dodecyl-phenylcarbamoylmethyl ammonium chloride ( c ), were synthesized and characterized. The surface tension and conductivity values were employed to investigate the absorption and micellization behavior of the three cationic surfactants. The results showed that the synthesized surfactants have shown a low critical micelle concentration (CMC) and a high adsorption efficiency (pC₂₀) compared with the traditional cationic surfactant of N,N-dimethyl-N-dodecyl-N-benzyl ammonium chloride ( BAC-12 ). The aromatic rings of the a , b , and c molecular structures were analyzed using the ¹H NMR spectra for electrostatic repulsion effects between hydrophilic headgroups. The size distribution of the micelles was derived using dynamic light scattering (DLS) techniques. In addition, the foaming ability of a , b , c , and BAC-12 was investigated and the antimicrobial activity of a , b , c , and BAC-12 against Escherichia coli, Staphylococcus aureus, and Bacillus subtilis was examined. The effects of amide bonds and aromatic rings on the surface properties and antimicrobial activity of a , b , and c were analyzed and compared with BAC-12 of the same alkyl chain length. The synthesized surfactants exhibited a high surface ability and better antibacterial activity compared with BAC-12 .     

An experimental study of interaction between surfactant and particle hydrogels

Polyacrylamide gel was synthesized to study interaction between surfactant and particle hydrogel. Surfactants used in this study include cationic surfactants, n-dodecylpyridinium chloride, (1-hexadecyl) pyridinium bromide; anionic surfactants, sodium salt of dodecylbenzene sulfonic acid, sodium 4-n-octyl benzene sulfonate and sodium branched alcohol propoxylate sulfate; and nonionic surfactants, Igepal^® CO-530, Tergitol^® NP-10 and Neodol^® 25-12. It has been found that, after swelling of the dry particles, surfactant concentration shows a substantial increase. Meanwhile, dynamic modulus (G′ and G") of the gels shows a significant decrease in the surfactant solutions. Based on the experimental results, a mechanism has been proposed to elucidate the reduction of the gel dynamic modulus. Furthermore, this mechanism was discussed through surfactant critical packing parameters (CPP) at the interface of the hydrogel particle and surfactant aqueous solution, and confirmed by recovery of the gel dynamic modulus after removal of the surfactant from the hydrogels.     

Corrosion inhibition by N‐(alkyloxycarbonylmethyl)‐N‐triethanol ammonium chloride with respect to the surface and thermodynamic properties

N‐[(octyloxycarbonylmethyl)‐ N‐triethanol ammonium chloride] (C₈ ), N ‐[(dodecyl‐oxycarbonylmethyl)‐ N‐triethanol ammonium chloride] (C₁₂ ) and N ‐[(hexadecyloxycarbonylmethyl)‐N ‐triethanol ammonium chloride] (C₁₆ ) were synthesized. Surface tension was measured in aqueous solution for different concentrations at 28, 38 and 48°C. Various surface properties of the synthesized surfactants were evaluated, particularly critical micelle concentration (CMC), efficiency (Π_CMC) as well as maximum surface excess (Γ_max) and minimum surface area (A_min). Micellization and adsorption in both liquid/air and liquid/solid interfaces thermodynamics were investigated. These products have pronounced surface activity and satisfactory corrosion inhibition of C‐steel in hydrochloric acid at 28, 38 and 48°C. © 1999 Society of Chemical Industry     

Synthesis and corrosion inhibition mechanism of ammonium-based ionic liquids on API 5L X60 steel in sulfuric acid solution

A novel class of four new-free-halide-ionic liquids (ILs) derived from ammonium was synthesized and characterized via spectroscopic methods such as ¹H NMR and ¹³C NMR. The synthesized compounds were evaluated as corrosion inhibitors (CIs) of API 5L X60 steel in 1 M sulfuric acid by means of the potentiodynamic polarization and weight loss techniques. The results confirmed that the inhibition efficiency displayed by the four ILs is a function of their concentration and molecular structure. The obtained inhibition efficiency (η) ranged from 51 to 89%, confirming that the new class of ILs is good for corrosion inhibition purposes. The analysis of the potentiodynamic results showed that these compounds inhibit the corrosion of steel, classifying them as mixed-type CIs. The adsorption process of these new CIs on the API 5L X60 steel surface, which obeyed the Langmuir isotherm, was found to be physical and chemical. The SEM and EDX analyses confirmed the protection of steel in the corrosive medium.