Effect of polyethyleneimine ion on the sorption of a reactive dye onto Leacril fabric: electrokinetic properties and surface free energy of the system

Data are presented on the kinetics, electrokinetics, and surface free energy in the process of adsorption of polyethyleneimine (PEI) as a pretreatment of Leacril, later dyed with the reactive dye Remazol Brilliant Blue R (RBBR). The electrokinetic potential of Leacril is negative, due probably to the presence of sulfonate and sulfate end-group onto Leacril fibers. The zeta potential of Leacril decreases in absolute value as a function of NaCl concentration in solution, probably because of compression of the electrical double layer. The zeta potential of Leacril as a function of the concentration of PEI in solution increases because of the adsorption of PEI ions through chemical reaction between the sulfonate end-groups of Leacril and the amine groups of PEI. The adsorption kinetics shows that an increase in the concentration of PEI, brings about an increase in the amount of RBBR adsorbed onto the fiber. This may be an indication of the chemical reaction between the reactive groups of the polyelectrolyte and dye molecules. The behavior of the surface free energy of the systems involved confirms these conclusions.     

Electrokinetic effect and surface free energy behavior in the adsorption process of a reactive dye onto Leacril pretreated with polyethyleneimine ion

In a previous paper, we studied the adsorption of a polyelectrolyte, polyethyleneimine ion (PEI), onto Leacril in order to increase the amount of the reactive dye Remazol Brilliant Blue R (RBBR) taken up by these fibers. We observed that this polycation changes the fibers zeta potential sign at low concentration, ca. 0.03 g/L, and thus the RBBR adsorption onto Leacril is improved when implementing the PEI treatment. The aim of this work is to study the PEI effect related to the amount of dye adsorbed by Leacril. For this purpose, we present data on streaming potential, adsorption isotherms, and surface free energy component determination as a function of the PEI concentration used in the pretreatment, as well as a function of the RBBR concentration used in the dyeing solutions. Adsorption experimental results show that the amount of RBBR taken by the fibers increases with the PEI concentration used in the pretreatment, and this effect becomes significant at higher concentrations of RBBR solution. The zeta potential increases to positive values in the range of low concentrations of dye solution when Leacril fibers have been pretreated with the polyelectrolyte. From surface free energy component determinations it is worth noting that the electron-donor component, gamma(-), decreases with the RBBR concentration in the treatment. The results we have obtained suggest that the interaction between the amine group of the PEI previously adsorbed and the reactive beta-sulfato-ethysulfonyl group of the dye can be responsible for the improvement in dye uptake.     

Study on QPVA/TEOS hybrid anion membrane functionalized with quaternary ammonium groups for adsorption of Rhodamine B from aqueous solutions

Quaternized poly(vinyl alcohol)/tetraethoxysilane hybrid membranes were prepared and their adsorbability for Rhodamine B from aqueous solution was investigated. Experimental parameters, which will affect Rhodamine B sorption, such as tetraethoxysilane contents, pH, contact time, initial concentration and temperature were studied. The research results revealed that adsorption effect of Rhodamine B was enhanced by the formation of organic–inorganic hybrid structure and the grafting of quaternary ammonium groups. The fitting result of kinetic data was revealed that the pseudo-second-order model best described the adsorption of Rhodamine B. The equilibrium data were fitted by three isotherm models, and the Temkin model gave the best fit result based on the adsorption equilibrium data. Also, the adsorption free energy showed that the mechanism of Rhodamine B adsorption onto the membrane was chemisorption. Thermodynamic parameters calculation results revealed that the adsorption process of Rhodamine B onto the hybrid membrane was endothermic and spontaneous. Moreover, the hybrid membrane was successfully utilized for successive five cycles for the adsorption–desorption of Rhodamine B.     

Kinetic and thermodynamic studies on the adsorption behavior of Rhodamine B dye on Duolite C-20 resin

The adsorption behavior of Rhodamine B dye from aqueous solutions was investigated onto the cation-exchange resin, Duolite C-20 (hydrogen form). The effects of various experimental factors; sorbent amount, contact time, dye concentration and temperature, were studied by using the batch technique. Lagergren pseudo-first-order equation shows good applicability with high correlation coefficients for all ranges of initial dye concentrations and at different temperatures. This equation was used to describe the kinetics of the dye adsorption process. The adsorption constants were evaluated by using both the Langmuir and Freundlich adsorption isotherm models. Thermodynamic parameters were obtained and it was found that the adsorption of Rhodamine B dye onto Duolite C-20 resin was an endothermic and spontaneous process at the temperatures under investigation.     

Time-resolved fluorescence anisotropy measurements of the adsorption of Rhodamine-B and a labelled polyelectrolyte onto colloidal silica

 The application of time-resolved fluorescence anisotropy measurements (TRAMS) to the investigation of the adsorption of the dye Rhodamine B and a Rhodamine B-labelled cationic polyelectrolyte onto colloidal silica (Ludox) is described. For Rhodamine B the time-resolved fluorescence anisotropy behavior observed can be interpreted using a model consisting of fluorophores with two distinct fluorescence decay lifetimes and two rotational correlation times corresponding to the fluorophore free in solution and bound to the Ludox. Details of the binding obtained from a global analysis of the data are reported. Restricted motion of the fluorescently labelled polyelectrolyte is also observ-ed on adsorption. The considerations for the general application of TRAMS for monitoring adsorption behavior are discussed. Received: 8 July 1998 Accepted: 10 August 1998     

Change of adsorption modes of dyes on fluorinated TiO2 and its effect on photocatalytic degradation of dyes under visible irradiation

Surface-fluorinated TiO2 (F-TiO2) particles were prepared via the HF etching method. The surface characteristics of fluorinated TiO2, the adsorption modes of dyes, and the reaction pathways for the photocatalytic degradation of dye pollutants under visible light irradiation were investigated. It was found that, in the treatment of TiO2 by HF etching, F(-) not only displaces surface HO(-) but also substitutes some surface lattice oxygen. Using zwitterionic Rhodamine B (RhB) dye as a model, the change of the adsorption mode of RhB on F-TiO2 relative to that on pure TiO2 was validated by adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and IR techniques for the first time. RhB preferentially anchors on pure TiO2 through the carboxylic (-COOH) group, while its adsorption group is switched to the cationic moiety (-NEt 2 group) on F-TiO2. Both the photocatalytic degradation kinetics and mechanisms were drastically changed after surface fluorination. Dyes with positively charged nitrogen-alkyl groups such as methylene blue (MB), malachite green (MG), Rhodamine 6G (Rh6G), and RhB all underwent a rapid N-dealkylation process on F-TiO2, while on pure TiO2 direct cleavage of dye chromophore ring structures predominated. The relationship between surface fluorination and the degradation rate/pathway of dyes under visible irradiation was also discussed in terms of the effect of fluorination on the surface adsorption of dyes and on the energy band structure of TiO2.     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

Electrokinetic and Thermodynamic Analysis of the Dyeing Process of Polyamide Fabric with Mordant Black 17

An electrokinetic and thermodynamic analysis of the dyeing process of polyamide 6.6 (nylon 6.6) by the dye Palatine chrome black (PCB) is described in the present work. The electrokinetic study was performed by means of electrophoretic mobility measurements on bare and dyed fiber. The most significant result is the increase in electrokinetic potential, zeta, toward more negative values as the dye concentration in the dispersion medium is raised. Given the molecular structure of PCB, which contains a sulfonate group per molecule, it is feasible that such increase in |zeta| is due to the adsorption of the negatively charged, dissociated dye entities. The uptake of PCB by the fiber is experimentally determined at two temperatures: the strong increase in the amount of dye incorporated into the fiber as the initial concentration of PCB is larger, and also the fact that higher temperatures favor the dyeing process is an indication of the existence of strong interactions between both interfaces. From a different point of view, the efficient coverage of Nylon by PCB is also demonstrated by the changes experienced by the surface free energy of Nylon upon treatment with PCB. Copyright 2001 Academic Press.     

Facile tailoring of film morphology and release properties using layer-by-layer assembly of thermoresponsive materials

Layer-by-layer self-assembly was used to prepare thermoresponsive thin films of poly(N-isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) (PAA) based on hydrogen bonding. The temperature of PNIPAAm adsorption was shown to significantly affect both the mass proportion of PNIPAAm in the film and the film surface morphology. When the adsorption was conducted at temperatures close to the lower critical solubility temperature of PNIPAAm, the amount of PNIPAAm in the film increased significantly (from 51 to 59%), and the total film mass increased by 30-40%. The films prepared at 30 degrees C also exhibited a lower surface roughness (1-2 nm) compared with 5-8 nm when prepared at 10 or 21 degrees C. The resulting multilayer films ([PAA/PNIPAAm]10) were capable of being reversibly loaded and unloaded with dye (Rhodamine B) by exposure to solutions at elevated temperatures. The rate of loading and release was shown to depend on both the solution temperature and film preparation temperature, leading to tunable loading/release properties.     

Nucleation of bulk phases in the HCl/H2O system

We report experimental results on the low-temperature uptake of HCl on H(2)O ice (ice). HCl was deposited on the surface at greater than monolayer amounts at 85 K, and the ice substrate was heated. The temperature dependence of the HCl vapor pressure from this phase was measured from 110 to 150 K, with the nucleation of a bulk hydrate phase observed at 150 K. Measurements were conducted in a closed system by simultaneous application of gas phase mass spectrometry and surface spectroscopy to characterize vapor/solid equilibrium and the nucleation of bulk hydrate phases. Combining the nucleation data reported here with data we reported previously (180 to 200 K) and data from two other laboratories (165 and 170 K), the thermodynamic boundaries for the nucleation of both the metastable bulk solution and bulk hydrate phases subsequent to monolayer adsorption of HCl have been determined. The nucleation of the metastable bulk solution phase occurs promptly at monolayer coverage at the ice/liquid coexistence boundary on the binary bulk phase diagram. The nucleation of the bulk hexahydrate occurs from this metastable solution along a locus of points defining a state of constant solution free energy. This measured free energy is -51.2 +/- 0.9 kJ/mol. Finally, the temperature dependence of the HCl vapor pressure from the low-temperature phase is reported here for the first time and is consistent with that of the metastable solution predicted by this thermodynamic model of uptake, extending the range of validity of this model of adsorption followed by bulk solution and hydrate nucleation to a lower bound in temperature of 110 K.     

Study of the surface properties and surface concentration of ionic liquid–alcohol mixtures

Surface properties for three binary mixtures containing a 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) and a long-chain alcohol (1-butanol, 1-pentanol and 1-hexanol) were determined by surface tension data at the following temperatures: (298.15, 308.15, 318.15, 328.15 and 338.15) K. The surface tension data over the entire mole fraction range are correlated by the Fu et al.(FLW) and Myers-Scott (MS) models. There is good agreement between the experimental data and the results of correlations for 15 binary systems (the three systems at five temperatures) with an average relative error below 1.5%. In addition, the UNIFAC group contribution method is applied for calculation of activity coefficients of components in solution. Moreover, the relative adsorptions of alcohol at the air/liquid interface are determined using Gibbs adsorption isotherm. The obtained results show that the values of adsorption for mixtures of alcohols/[BMIM][SCN] increase with increasing the alkyl chain length of alcohol and decreasing temperature.     

A cyclic voltammetry study of the adsorption of alcohol dehydrogenase (HLADH) onto a platinum electrode

A cyclic voltammetry study of the interfacial behaviour of horse liver alcohol dehydrogenase (HLADH) at a Pt surface in a phosphate buffer solution pH 7.0 over the temperature range 273 to 353 K is presented. The surface charge density, resulting from protein adsorption, was shown to be directly proportional to the amount of adsorbed protein (surface concentration). HLADH exhibits very high affinity towards adsorption onto a Pt surface via chemisorption. The Langmuir isotherm was employed for modeling the adsorption process and the values of the Gibbs free energy, enthalpy and entropy of adsorption were calculated. The thermodynamic data suggested that disruption of tertiary structure of the protein occurs upon adsorption at the Pt surface and that the breaking of intramolecular interactions during the adsorption governs the rate of the process.     

玻璃硅烷化处理对罗丹明6G和亚甲基蓝吸附行为的影响

利用六甲基二硅烷胺对平面玻璃光波导(高折射率透明导光薄膜介质)进行硅烷化处理, 得到水接触角大于90°的疏水表面. 然后使用时间分辨光波导分光光谱技术研究水溶液中的罗丹明6G (R6G)和亚甲基蓝(MB)分子在疏水玻璃表面的吸附行为, 并与亲水玻璃条件下测得的结果进行对比. 对利用疏水玻璃光波导测得的R6G的吸附-脱附动力学曲线进行Langmuir拟合得到了R6G的吸附速率常数, 脱附速率常数以及吸附自由能. 并且发现与亲水玻璃情况相比, 吸附速率常数增大, 脱附速率常数减小, 吸附自由能更负. 在疏水玻璃表面形成的R6G和MB吸附层的吸光度与亲水玻璃情况相比显著升高, 表明这两种分子更倾向于吸附在疏水玻璃表面. 实验结果还发现玻璃硅烷化处理能够有效抑制这两种染料分子在表面的聚合反应.     

阴离子表面活性剂存在下吖啶橙—罗丹明B混合体系能量转移研究

本文以吖啶橙和罗丹明Ｂ作为能量转移中的给予体和接受体，分别探讨了不同阴离子表面活性剂对染料问能量转移影响。从染料分子所处微环境变化的角度阐明了分子聚集状态的变化是影响能量转移效率的重要因素。     

A simple method for removal of toxic dyes such as Brilliant Green and Acid Red from the aquatic environment using Halloysite nanoclay

This project explains an easy, simple and eco-friendly method to remove some toxic dyes like Brilliant Green and Acid Red from aquatic solution by technique of solid-phase extraction that uses Halloysite nanoclay eco-friendly solid phase as absorbent surface for adsorption of dye. The physical properties of the HNC such as scanning electron microscopy, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and surface area analysis were studied. The best conditions like pH of the solution, HNC weight, contact shaking time, the temperature of the solution, and ionic strength were investigated for removal effectiveness. The experimental data of the adsorption process showed that HNC can remove most of the dyes within 30 min, with an adsorption capacity of 12.5 mg/g for A.R dye and 13.9 mg/g for B.G dye on HNC solid phase at optimum conditions. The removal process of dyes on HNC was studied kinetically and thermodynamically, and the data confirms that the pseudo-second-order kinetic model was able to describe the adsorption process. Thermodynamic data confirms the process was spontaneous andexothermic in nature for A.R dye, while was spontaneous and endothermic in nature for B.G dye. Finally, the effectiveness of HNC was inspected by removing dyes from three various real samples, and the results showed high performance in removing dyes on HNC for four consecutive cycles.     

照相光谱增感染料及其组合在溴化银表面的吸附及吸附热测量

本文研究了三个光谱增感染料及其组合在一些溶液中的吸收光谱和吸附态染料的反射光谱,得到25℃在几种溶剂的溴化银分散系中的吸附等温线,并采用精密量热技术测量了微小吸附热效应,得到25±0.01℃染料Ⅰ在溴化银水悬浮液中被吸附的等位摩尔吸附焓△H₂₉₈-(335±2.5)kJ/mol(表面覆盖度θ=0.94)。结合对染料组合的光吸收、吸附以及吸附热等的测试结果,对照相乳剂生产中采用的先加入感绿染料Ⅱ、Ⅲ,后加入感红染料Ⅰ的步序,从吸附角度作了初步的理论探讨。研究结果也表明,精密量热技术与光吸收测量等手段相结合,将有助于在乳剂制备过程中分析研究染料的增感效果。     

Theoretical and experimental approach of inhibition effect by sulfamethoxazole on mild steel corrosion in 1‐M HCl

The inhibition effect of sulfamethoxazole on mild steel corrosion in 1‐M hydrochloric acid solution is investigated by electrochemical and quantum chemical measurements. Electrochemical polarization studies show that sulfamethoxazole acts as a mixed‐type corrosion inhibitor. The adsorption of the inhibitor on mild steel in 1‐M hydrochloric acid system is studied at different temperatures (303‐333 K). The adsorption of sulfamethoxazole on mild steel surface is an exothermic process and obeys the Temkin adsorption isotherm. Based on the potential of zero charge values and quantum chemical parameters, the mechanism of adsorption is proposed.     

Thermodynamic properties and phase transtions in the H2O/CO2/CH4 system

The availability of free energy densities as functions of temperature, pressure and the composition of all components is required for the development of a three-component phase field theory for hydrate phase transitions. We have broadened the extended adsorption theory due to Kvamme and Tanaka (J. Phys. Chem., 1995, 99, 7114) through derivation of the free energy density surface in case of CO(2) and CH(4) hydrates. A combined free energy surface for the liquid phases has been obtained from a SRK equation of state and solubility measurements outside hydrate stability. The full thermodynamic model is shown to predict water-hydrate equilibrium properties in agreement with experiments. Molecular dynamics simulations of hydrates in contact with water at 200 bar and various temperatures allowed us to estimate hard-to-establish properties needed as input parameters for the practical applications of proposed theories. The 5-95 confidence interval for the interface thickness for the methane hydrate/liquid water is estimated to 8.54 A. With the additional information on the interface free energy, the phase field theory will contain no adjustable parameters. We provide a demonstration of how this theory can be applied to model the kinetics of hydrate phase transitions. The growth of hydrate from aqueous solution was found to be rate limited by mass transport, with the concentration of solute close to the hydrate approaching the value characterizing the equilibrium between the hydrate and the aqueous solution. The depth of the interface was estimated by means of the phase field analysis; its value is close to the interface thickness yielded by molecular simulations. The variation range of the concentration field was estimated to approximately 1/3 of the range of the phase field.     

Aggregation of rhodamine 3B adsorbed in Wyoming Montmorillonite aqueous suspensions

The adsorption of Rhodamine 3B (R3B) molecules in Wyoming Montmorillonite (Mont) particles suspended in water was studied by electronic absorption spectroscopy. Several adsorbed R3B species in the Mont tactoids were characterized from the observed changes in the absorption spectra by increasing the relative dye/clay concentration and the stirring time of the samples. R3B molecules can be adsorbed as monomeric units both in the water/clay interface and in the interlayer space, and head-to-tail R3B dimers and trimers were present in the external surface of Mont. The formation of internally adsorbed R3B monomers by the migration of the externally adsorbed species to the interlayer space leads to the deaggregation of the dye molecules in the external surface.     

Dyeing of PA 6.6 fibers

Dyeing fibers at low temperatures has many advantages such as savings in energy and avoiding alterations to the physical properties of the fibers being dyed or other fibers also present in blends. The problem of low temperature dyeing in synthetic fibers is that it difficults the dye diffusion into the fiber. In the case of polyamide 6.6 microfibers, by using benzyl alcohol as an auxiliary dyeing, it was shown that good diffusion was obtained for the dye exhaustion with metal complex dyes at temperatures more than 30°C below the normal dyeing temperature for the dye exhaustion with metal complex dyes. Using thermal analysis methods these results were shown to be caused by the lowering of the T _g of the fiber when in the presence of benzyl alcohol. This revised version was published online in July 2006 with corrections to the Cover Date.