Efficiency of Laundry Polymers Containing Liquid Detergents for Hard Surface Cleaning

Three water soluble laundry polymers were employed for the first time in liquid detergent formulations for hard surface cleaning. The polymers included in the formulations were the sodium salt of maleic acid/olefin copolymer (P1, anionic), polyethyleneimine (P2, cationic), and polyethylene glycol‐g‐vinyl acetate (P3, nonionic). Commercially available surfactants (C₁₀ Guerbet alcohol alkoxylate (FAEO), caprylyl/decyl glucoside (APG), and the sodium salt of ethoxylated alkyl ether sulfate (SLES) were chosen to formulate bathroom, kitchen, and all‐purpose cleaners, which provide the desired broad of pH range for hard surface applications. Their hard surface cleaning efficiencies were also compared with an amphoteric polymer (amino modified polycarboxylate, P4) as amphoteric polymers are the most suitable structures for hard surface cleaning. The standard test method and the cleaning device, the so‐called cleaning robot, were used to investigate the primary cleaning performances and synergies of the chosen polymers in a hard surface cleaners system. Secondary cleaning performance tests, which indicate the effects of the hard surface cleaners on surface modification, were also performed. The results revealed that the formulations containing P3 and P4 gave the better cleaning performance for primary cleaning tests whereas only P4‐containing formulations showed the significant results for secondary cleaning tests.     

Effects of nonionic surfactant on the rheological property of associative polymers in complex formulations

The rheological properties of hydrophobically modified ethoxylated urethane (HEUR) were investigated in the presence of a nonionic surfactant, polyoxyethylene stearyl ether (C₁₈(EO)₂₀). The presence of nonionic surfactants played an important role in tuning the rheological properties of HEUR aqueous solutions. Observing both plateau modulus and viscoelastic relaxation time of HEUR aqueous solutions with varying the concentration of C₁₈(EO)₂₀ allowed us to demonstrate that C₁₈(EO)₂₀ readily interacts with the hydrophobic segments of HEUR polymers, which eventually formed a strong micellar network. Moreover, the micellar network formed at a critical concentration of C₁₈(EO)₂₀, ∼0.6% w/v, was indeed stable against both ionic strength and pH in the aqueous medium and complex formulations, such as a colloid suspension and an oil-in-water emulsion, thus providing more practical applications as thickeners for a wide variety of complex formulations.     

Polymeric surfactants for enhanced oil recovery. Part V: Prediction models for the effect of temperature and length of polyoxyethylene chain or hlb on surface and thermodynamic properties of some ethoxylated polymeric nonionics

Several equation models were investigated to find the relationship between temperature (T). number of ethylene oxide (EO) units (n) or the hydrophile-lipophile balance (HLB) and the surface and thermodynamic properties of some ethoxylated alkylphenol-formaldehyde polymeric nonionic surfactants. These properties include critical micelle concentration (CMC), free energy of micellization (ΔG_mic), surface tension at CMC (7_CMC), effectiveness (γ_CMC) and efficiency (pC₂₀) of surfactant to reduce the surface tension of water. The values of the ratio CMC/C_{2(π = 20)} were also considered. The linear multiple regression technique was employed to determine the parameters of the equations and to choose the best forms with the highest values of R² and F-ratio which reflect the goodness and the reliability of the fit.     

Solubilization of phospholipid bilayer caused by surfactants

The interaction of surfactants with liposomes eventually leads to the rupture of such structures and the solubilization of the phospholipid components. In this paper, solubilization is regarded as a decrease in light scattering of liposome suspensions. To this end, in accordance with the nomenclature, adopted by Lichtenberg, three parameters were considered as corresponding to the effective surfactant/lipid molar ratios (Re) at which light scattering starts to decrease, Re_sat; reaches 50% of the original value, Re₅₀; and shows no further decrease, Re_sol. These parameters corresponded to the Re at which the surfactant (i) saturated the liposomes, (ii) resulted in a 50% solubilization of vesicles and (iii) led to a total solubilization of liposomes. The surfactants tested were the nonionic surfactant octylphenol ethoxylated with 10 units of ethylene oxide or Triton X-100 (OP-10EO), two anionic surfactants, sodium dodecyl sulfate and sodium dodecyl ether sulfate, and an amphoteric surfactant dodecyl betaine (D-Bet). Unilamellar liposomes formed by egg phosphatidylcholine containing increasing amounts of phosphatidic acid were used. The Re parameters were the lowest for D-Bet, followed by OP-10EO, whereas the anionic surfactants always showed the highest values regardless of the electrical charge of the lipid bilayers. These parameters seem also to be inversely related to the critical micelle concentration (CMC) of the surfactant, except for OP-10EO. Moreover, the CMC values of the surfactant/lipid systems at 0.5 mM lipid concentration corresponded in all cases to the surfactant concentration at which liposomes were saturated by surfactants. As a consequence, this ratio can be regarded as an interesting parameter associated with the mixed micelle formation in liposome solubilization.     

Waterborne latex coatings of color: II. Surfactant influences on color development and viscosity

A matrix of coating variables, nonassociative versus associative thickeners, different latex median particle sizes, individual surfactants and colorants [carbon black (CB), red, and yellow pigments], was examined for their influence on variances in coatings rheology and color development. Within the different coating groups, the variable of interest in this study was the surfactant added to the colorant formulation. In all three colorant formulations, sodium dodecyl sulfate (an anionic surfactant) provided poorer color development (CD) than in applied formulations containing an equivalent nonylphenol oxyethylene (EO) surfactant. In CB formulations, nonionic surfactants with higher EO content provide improved color development at low (2 mM) concentrations, but near equality in CD is achieved with low EO surfactants at higher concentrations. In contrast to CB formulations, red and yellow colorants exhibit good color development with high EO content nonionic surfactants only at low nonionic surfactants concentrations. This variance appears to be related to the interactions of surfactants with inorganic pigments (talc and laponite) in the colorant formulation. The coating’s rheology is related to latex, thickeners, and surfactant components of the paint, as has been noted in previous studies, but not to the nature of the color pigment. The viscosity of the hydroxyethyl cellulose (nonassociative type) and HEUR (associative type) thickened paint decreased with colorant addition due to dilution effects. There were no unusual deviations with the NP(EO)_x surfactants, except when a large hydrophobe nonionic surfactant [e.g., C₁₈H₃₇(EO)₁₀₀] is added. In HEC thickened coatings, the viscosity decreases when C₁₈H₃₇-(EO)₁₀₀ is in the colorant due to that surfactant inhibiting depletion flocculation. In the C₁₈H₃₇(EO)₁₀₀ coatings containing the HEUR thickener, significant increases in viscosity were observed, above the dilution values observed with the colorant addition. This is related to the viscosity maximum in the low concentration of HEUR with the C₁₈H₃₇(EO)₁₀₀ surfactant. Color development is independent of the viscosity profile of the coating. Presented in part at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2003 in Philadelphia, PA.     

Effect of Polyoxyethylene Chain Length on the Physicochemical Properties of N,N‐Dimethyl‐N‐dodecyl Polyoxyethylene Amine Oxide Hybrid Surfactants (C12EOnAO,with n = 1–4)

In order to determine the structure‐performance relationship of nonionic‐zwitterionic hybrid surfactants, N,N‐dimethyl‐N‐dodecyl polyoxyethylene (n) amine oxides (C₁₂EO_nAO) with different polyoxyethylene lengths (EO_n, n = 1–4) were synthesized. For homologous C₁₂EO_nAO, it was observed that the critical micelle concentration (CMC), the maximum surface excess (Γ_m), CMC/C₂₀, and the critical micelle aggregation number (N_m,c) decreased on going from 1 to 4 in EO_n. However, there were concomitant increases in surface tension at the CMC (γ_CMC), minimum molecular cross‐sectional area (A_min), adsorption efficiency (pC₂₀), and the polarity ([I₁/I₃]_m) based on the locus of solubilization for pyrene. The values of log CMC and N_m,c decreased linearly with EO_n lengthening from 1 to 4, although the impact of each EO unit on the CMC of C₁₂EO_nAO (n = 1–4) was much smaller than that typically seen for methylene units in the hydrophobic main chains of traditional surfactants. Compared to the structurally related conventional surfactant N,N‐dimethyl‐N‐dodecyl amine oxide (C₁₂AO), C₁₂EO_nAO (n = 1–4) have smaller CMC, A_min, and CMC/C₂₀, but larger pC₂₀, Γ_m, and N_m,c with a higher [I₁/I₃]_m. This may be attributed to the moderately amphiphilic EO_n (n = 1–4) between the hydrophobic C₁₂ tail and the hydrophilic AO head group.     

Synergism and Performance Optimization in Liquid Detergents Containing Binary Mixtures of Anionic–Nonionic, and Anionic–Cationic Surfactants

In this paper evaluation of surface active and application properties in liquid detergent formulations containing binary mixtures of anionic–nonionic, and anionic–cationic surfactants is discussed. Surfactants used include: linear alkylbenzene sulfonate (LAS), alcohol ether sulfate (AES-2EO), alcohol ethoxylate (AE-7EO), lauryl dimethyl amine oxide, and alkyl hydroxyethyl dimethyl ammonium chloride (AHDAC). Surface active parameters relating to the effectiveness and efficiency of surface tension reduction were determined from the surface tension data. Non-ideal solution theory was used to determine the degree of interactions between the two surfactants, and the conditions under which a mixture of two surfactants show synergism in surface active properties. Our data indicated that synergism in mixed surfactants increases with the degree of charge difference between the surfactants. In both mixed micelle and mixed monolayer formation, the degree of interactions between the two surfactants in the mixture increased in the following order: LAS/AE < AES-2EO/amine oxide < AES-2EO/AHDAC. This synergistic behavior as presented in this paper leads to unique application properties and improved performance in terms of foam volume, and soil removal which has applications in formulation of dishwashing liquids, and laundry detergents.     

Dissolution of Soap Scum by Surfactant Part I: Effects of Chelant and Type of Soap Scum

The equilibrium solubilities of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were measured in aqueous solutions containing three different types of surfactants: methyl ester sulfonate (MES) as an anionic; alcohol ethoxylate (EO9) as a nonionic; and dimethyldodecylamine oxide (DDAO) as an amphoteric with and without a chelating agent [disodium ethylenediaminetetraacetate (Na₂EDTA)]. The solubility of calcium soap scum was generally higher than that of magnesium soap scum, the exception being some DDAO systems. The use of the DDAO surfactant with the Na₂EDTA chelating agent at high pH gives the highest solubilities of both studied soap scums. The soap scum solubility is on the order of 2,000 times that in water at high pH. The DDAO is the most effective surfactant under all conditions. The MES is more effective than the EO9 at low pH with the opposite trend observed at high pH. The synergism from added chelant is generally greater at higher pH and is greatest for DDAO followed by EO9.     

Forecasting the cloud point of alkoxylated nonionic surfactants

The highest effectiveness of detergency for nonionic surfactants is observed in the proximity of the cloud point. This phenomenon is primarily influenced by surfactant molecular structure, such as carbon chain length and type of the hydrophilic components. Target of this investigation is to identify a relationship between the cloud point and the structure of nonionic surfactants based on ethoxylated (C_nE_m), ethoxylated-propoxylated (C_nE_mP_p) and propoxylated-ethoxylated (C_nP_pE_m) fatty alcohols. Three hundred and fifty nonionic surfactants have been prepared for this purpose. These surfactants differ in the C-chain lengths, C₄/C₆ to C₂₀/C₂₂, and the amount of ethylene oxide (EO range [n] 2–22 ethoxylation) and propylene oxide (PO range [p] 0–12 propoxylation) moieties. Mapping the differences in the performance allows us to propose a high-accuracy topological model describing the structure influence on the cloud point.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.     

Experimental Study of CMC Evaluation in Single and Mixed Surfactant Systems, Using the UV–Vis Spectroscopic Method

In this study, the critical micellar concentration (CMC) of anionic, cationic and nonionic surfactants was determined using the UV–Vis spectroscopic method. Sodium lauryl sulfate (SDS) as anionic, hexadecyl-trimethyl-ammonium bromide as cationic, tert-octylphenol ethoxylates TOPEON (with N = 9.5, 7.5 and 35) and lauryl alcohol ethoxylate (23EO) as nonionic surfactants have been used. Concentration of surfactants varies both from below and above the CMC value in the pyrene solution. In addition, the amount of the CMC was determined using the values from the data obtained from the graph of absorbance versus concentration of surfactants. A comparative study was conducted between the results of the present study and the literature which shows a good agreement, in particular for TOPEO9.5 and LAEO23. Furthermore, the CMC value of SDS (as an ionic surfactant) in the presence of nonionic surfactants was also examined. The result reveals that with addition of small amount of nonionic surfactant to the anionic SDS surfactant, a decline in the CMC value of the anionic–nonionic system relative to the CMC of pure anionic surfactant was observed. In addition and for the first time, the effect of UV irradiation on the size of the micelle formations was studied. It was found that UV irradiation causes the formation of smaller micelles which is of prime concern in membrane technology.     

Performance of alpha olefin sulfonates derived from ziegler olefins in light duty liquid detergents

Single carbon number olefins derived from Ziegler technology were sulfonated in a continuous fallingfilm SO₃ reactor. The resulting alpha olefin sulfonate (AOS) was evaluated in a dishwashing test at several water hardnesses. Statistical analysis of the data led to the selection of compositions suitable for hand dishwash applications. AOS, prepared by sulfonating a blend of C₁₄ and C₁₆ olefins, was evaluated for hand dishwashing efficiency in a ternary mixture consisting of AOS, an alcohol ether sulfate and monoethanolamide. Regression equations calculated from the data permit the prediction of performance levels for all practical combinations of the three ingredients. The effect of unreacted olefin on AOS dishwash performance was also determined. With a binary blend of AOS and monoethanolamide it was shown that up to 5% free oil (based on AOS active) could be tolerated without significant deleterious effect.     

Alpha olefin sulfonates from a commercial SO3-Air reactor

Alpha olefin sulfonate (AOS) can be made by SO₃-air sulfonation of straight chain alpha olefins followed by saponification of the neutralized product. The sulfonation step forms unsaturated sulfonic acids, sultones and sultone sulfonic acids. Hydrolysis of the various sultones yields a mixture of unsaturated and hydroxy sulfonates. Sulfonation of commercial mixtures of straight chain alpha olefins in a large-scale SO₃ falling film unit has given AOS of 1.5–3.0% oil based on active content and tristimulus color of about 40% saturation (2% solution) which is readily bleachable with 1–3% NaOCl to about 10–15% saturation. Performance of AOS made from C₁₅−C₁₈ alpha olefin is comparable to that of the high-foaming C₁₁−C₁₄ LAS in both detergency and dishwashing foam. It is superior to similar products made from internal straight chain olefins. The product shows a low order of toxicity and biodegrad-ability slightly better than that of LAS. A C₁₅−C₁₆ AOS blend is especially attractive in liquid detergent formulations. Presented at the AOCS Meeting, Los Angeles, April 1966.     

AOS — An anionic surfactant system: Its manufacture,composition, properties,and potential application

Several sulfonation parameters, believed to be critical to the manufacture of good quality a-olefin sulfonate (AOS), are related to product color and conversion. The interfacial properties for single carbon number AOS and the major components comprising AOS are investigated. Results, based on surface activity, indicate that AOS in the molecular weight range from C₁₄ through C₁₈ should be of value in formulating efficient cleaning agents. The data show that AOS is more effective for lowering Crisco®/solution interfacial energy than the more commonly used surfactants. The alkene-1-sulfonate component of AOS was found to be most effective in lowering interfacial energy with the hydroxyalkane-1-sulfonate component being significantly less effective but still more effective than alcohol ether sulfate or linear alkylbenzene sulfonate of comparable molecular weight. Hand dishwashing efficacy was found greatest for the hydroxyalkane-1-sulfonate component of AOS, but combinations of hydroxyalkane-1-sulfonates and alkene-1-sulfonates were shown to be synergistic for laundering applications. The presence of the -OH group in the hydroxyalkane sulfonate structure was shown to increase solubility and lower surface activity significantly more than the presence of unsaturation in the alkene sulfonate. Long, single branching in the a-olefin sulfonate and random internal olefin sulfonate are shown to reduce drastically the surface activity. The hydroxyalkane and alkene-1-sulfonates were rapidly biodegraded. Disulfonates and long, singly branched sulfonate were more slowly degraded. Both 1,3-sultones and 1,4-sultones were found to biodegrade rapidly.     

Advanced synthesis for monodisperse polymer nanoparticles in aqueous media with sub-millimolar surfactants

Highly monodisperse polystyrene nanoparticles with mean diameters of less than 100 nm are synthesized via aqueous emulsion polymerization using an amphoteric initiator (VA-057) in the presence of sub-millimolar concentrations of anionic surfactant. Since the net charge on the initiator is almost zero at neutral pH, the resultant latex particle size is mainly determined by surfactant adsorption. Polymerizations were performed in the presence of a range of anionic surfactants with differing critical micelle concentrations (CMC) by varying the concentrations of surfactant, initiator and monomer, and also the ionic strength. Sodium dodecyl benzene sulfonate (SDBS), sodium hexadecyl sulfate (SHS), and sodium octadecyl sulfate (SOS) have relatively low CMCs and so enable formation of highly monodisperse nanoparticles at relatively low (sub-millimolar) surfactant concentrations, C_S (i.e. below the CMC in each case). Empirically, it was found that the particle number, N_p, and coefficient of variation of the particle size, C_V, were strongly dependent on the C_S/CMC ratio: N_p increased almost in proportion with the square of this ratio, while the C_V exhibited a minimum at approximately C_S/CMC = 0.20. Higher ionic strength reduced the particle size, which is consistent with the above relationship because the addition of salt lowers the CMCs of ionic surfactants. Polymer latex particles produced using such formulations form highly regular, close-packed colloidal arrays.     

Sodium Alkyl Ether Sulfonates (SAES): Dual Anionic‐Nonionic Behavior in Synthetic Brine Having High Salinity and Hardness

Due to the presence of non‐sulfonated residual alkyl ether (AE), sodium alkyl ether sulfonate (SAES) may exhibit clear point‐cloud point solubilization behavior in brine. Accordingly, the effect of temperature on the compatibility of iC17EOxS (x = 7 and 10), nC₁₇EO10S, along with their analogous nonionic surfactants iC₁₇EOxH (x = 7 and 10) and nC17EO10, in addition to iC9EO14 in brine has been investigated. Depending on their molecular structures, these surfactants exhibited concentration‐dependent clear point and cloud point solubilization behavior. The cloud point was associated with the AE component whereas the clear point was attributed to the sulfonated one. Interestingly, an increase in the cloud point of the nonionic component with respect to the corresponding nonionic AE (100 % active) was observed. Adding iC9EO14 (100 % active) to iC17EO7S (x_an = 0.0–0.362) resulted in a significant decrease in the clear point of iC17EO7S from above 100 °C to below 22 °C with a concomitant increase in iC17EO7/iC9EO14 mixture cloud point from 68 °C. (x_an = 0) to 72 °C (x_an = 0.325). This relatively modest increase by 4 °C was attributed to the interrelationship of different competitive mechanisms, namely an increase in mixed micelle charge with increasing x_an, the dehydration of OE groups via ion (SO₃^?)‐dipole (O → CH₂) interactions, and possible shielding of SO₃^? groups by iC9EO14 nearby extended EO groups. To the best of our knowledge, this is the first instance where dual anionic‐nonionic solubilization behavior of SAES in brine characterized by high salinity and hardness is being reported.     

Dissolution of Soap Scum by Surfactants. Part III. Effect of Chelant Type on Equilibrium Solubility and Dissolution Rate of Calcium and Magnesium Soap Scums in Various Surfactant Systems

Soap scum can be effectively removed by using an appropriate surfactant with a chelating agent at a high solution pH. The equilibrium solubilities and dissolution rates of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were investigated in aqueous solutions containing three different types of surfactants [methyl ester sulfonate (MES) as an anionic surfactant; alcohol ethoxylate (EO9) as a nonionic surfactant; and dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant] in the presence of different biodegradable chelants: trisodium ethylenediamine disuccinic acid (Na₃EDDS) and tetrasodium glutamate diacetic acid (Na₄GLDA) compared with disodium ethylenediamine tetraacetate (Na₂EDTA), a chelant with poor biodegradability. The highest equilibrium solubility and dissolution rate of either soap scum were observed at high pH in the DDAO system with Na₄GLDA. In addition, the calcium soap scum had a similar to higher equilibrium solubility and a higher dissolution rate constant as compared with the magnesium soap scum.     

Studies on Surfactant–Ionic Liquid Interaction on Clouding Behaviour and Evaluation of Thermodynamic Parameters

The present study investigates the effect of tetraethyl ammonium tetrafluoroborate [TEA(BF₄)] ionic liquid (IL) on the cloud point (CP) of the following nonionic surfactants in aqueous solution: ter‐octylphenol ethoxylates with 9.5 and 4.5 ethylene oxide groups (abbreviated TOPEO9.5 and TOPEO4.5, respectively), cetyl alcohol ethoxylate with 10 ethylene oxide groups (C16EO10), and sorbitan monolaurate and monooleate both with 20 ethylene oxide groups (SMLEO20 and SMOEO20, respectively) in aqueous solutions. The thermodynamic parameters of these mixtures were calculated at different IL concentrations. The CP of most of the tested nonionic surfactants increased with the increment of IL concentrations with the exception of C16EO10 for which it decreased. The solubility of a nonionic surfactant containing polyoxyethylene (POE) hydrophilic chain was considered as maximum at the CP, hence the thermodynamic parameters were calculated at the same temperature. The results showed that the standard Gibbs free energy (?G_CP⁰), the enthalpy (?H_CP⁰) and the entropy (?S_CP⁰) of the clouding phenomenon were found to be positive for ethoxylated octylphenol and sorbitan esters, whereas ?H_CP⁰ and ?S_CP⁰ were found to be negative for C16EO10. It was found that the overall clouding process is endothermic for ethoxylated octylphenol and sorbitan esters and exothermic for C16EO10. For all the studied systems, ?H_CP⁰ > T?S_CP⁰ indicated that the process of clouding is guided by both enthalpy and entropy. The positive value of standard Gibbs free energy (?G_CP⁰) for the all mixed systems indicated that the process proceeds non‐spontaneously. The ?G_CP⁰ decreased with increasing IL concentration for all the nonionic surfactants; however, it decreased with increasing surfactant concentration for TOPEO9.5, C16EO10, and SMOEO20, and increased with increasing surfactant concentration for TOPEO9.5 and SMLEO20.     

Micelle formation in mixtures of nonionic and anionic detergents

This paper describes the effect of a homologous series of polyoxyethylene n-dodecanols on the critical micelle concentration (CMC) of sodium n-dodecyl alcohol sulfate as a function of composition of the mixtures and temperature. The CMC of the nonionic component of the mixed micelles is about one-hundredth of that of the anionic. Only a gradual increase in the CMC values of the mixed micelles above the values of the nonionic components was observed in the composition range of 0–90 mole % anionic detergent. This is followed by an abrupt transition to the high CMC values of the anionic component. The gradual increase of the CMC values in the range below 90 mole % anionic detergent of n-dodecanol+ 4 EO exceeds that of the higher homologs containing 7, 23 and 30 ethylene oxide units. It is postulated that the degree of ionic repulsion of the ionic component in mixed micelles is markedly decreased as the proportion of nonionic component reaches a threshold range of 10 mole %. This effect is more pronounced with large ethylene oxide coils operating at the periphery of the micelle core than with short ethylene oxide coils. Thermodynamic data have been included.     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.