Adsorption of cationic polyelectrolyte onto a model carboxylic latex and the influence of adsorbed polycation on the charge regulation at the latex surface

 Adsorption of a well-characterized cationic polyacrylamide (CPAM) onto the surface of a model colloid (monodisperse polystyrene latex with carboxylic functional groups) was studied over a wide range of pH (4–9) and KCl concentration (c _s =10^-3–0.3 M). The surface charge density of the latex particles with and without adsorbed CPAM was also measured over the same range of electrolyte compositions. The adsorbed amount of CPAM increases with increase in c _s and pH. The polyelectrolyte adsorption alters substantially the surface charge density of the latex particles as compared to the polymer-free case. A large overcompensation of the surface charge by the adsorbed polyelectrolyte is established at high c _s and low pH. A qualitative explanation of the observed features is put forward. Received: 3 December 1996 Accepted: 20 January 1997     

Adsorption Mechanism of Comb Polymer Dispersants at the Cement/Water Interface

Comb polymers are commonly used as dispersants to stabilize highly concentrated cement suspensions. The effectiveness of such polymeric additives to stabilize these suspensions is determined to a large extent by the amount adsorbed. In this study we investigated the adsorption characteristics of various comb dispersant containing different graft densities on surfaces of cement particle. The effect of inorganic salts on their adsorption was also examined in order to elucidate their adsorption mechanism. The results show that the adsorption of comb polymer dispersants on cement surface conforms approximately to Langmuir's adsorption isotherm and the characteristic plateau A _s and adsorption free energy ΔG_ads are largely dependent on the anionic group content of the comb polymers. The A _s and ΔG_ads increase with increasing anionic group content. This information suggests that the adsorption of comb polymers on cement surfaces is dominated by electrostatic interaction between COO-groups on the comb polymers and the positive surface of the cement. This conclusion is supported by effects of inorganics such as calcium and sulfate ions, and diffuse reflectance FTIR spectroscopy. The implication of results for tuning polymers for the required performance in cement manufacture should be noted.     

Mixed micellization and surface properties of non-ionic/cationic surfactants

We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C₁₂) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γ_cmc), Krafft Temperature (T_K), maximum excess concentration (Γ_max), minimum surface area per molecule (A_min), surface pressure at the CMC (П_cmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f₁(ISO-DIC C₁₂) and f₂ (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants.     

季铵盐三聚表面活性剂在空气-水界面上单分子膜的崩溃压和分子极限面积

利用Langmuir膜天平研究了季铵盐三聚表面活性剂12-2-12-2-12在空气-水界面单分子膜的表面压-分子面积(π-A)等温线, 得到它的崩溃压对应的表面张力g_collapse和分子极限面积A_limit. 与12-2-12-2-12溶液临界胶束浓度对应的表面张力g_cmc和由Gibbs吸附方程得到的分子平均面积A_cmc相比较, 发现A_limit＜A_cmc, 而且g_collapse＞g_cmc. 分析12-2-12-2-12单分子膜的表面压随时间的衰减, 表明这个现象是由于表面活性剂从铺展单分子膜向水中溶解造成的, 而且初始表面压越大, 表面压的衰减越快.     

Application of hydrophobically modified water‐soluble polyacrylamide conjugated with poly(oxyethylene)‐co‐poly(oxypropylene) surfactant as emulsifier

Hydrophobically modified polyacrylamide (PAAm) was prepared by grafting PAAm with block copolymer of poly(ethylene oxide) and poly(propylene oxide), PEO‐PPO‐PEO, by melt method in the presence of benzoyl peroxide as initiator. The chemical structure of the graft copolymer was determined by FTIR and ¹HNMR analyses. The surface tension, critical micelle concentration, and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration (Γ_max), the area per molecule at interface (A_min), and the effectiveness of surface tension reduction (Π_CMC) were determined at different temperatures from the adsorption isotherms of the prepared surfactants. The prepared surfactant was tested as emulsifier for water with xylene, cyclohexane, or petroleum crude oil synthetic emulsions. Copyright © 2010 John Wiley & Sons, Ltd.     

Estimation of morphology of composite polymer emulsion particles by the soap titration method

The occupied area (A_m) of a sodium dodecyl benzene sulfonate molecule adsorbed on particles was measured by the soap titration method. The A_m values are 214, 133, and 53 Ų for poly(methyl acrylate) (I), poly(methyl methacrylate) (II), and polystyrene (III), respectively. For methyl metharylate-styrene copolymer emulsions the additivity was established between the A_m value and copolymer composition. Composite emulsion particles consisting of I/II, I/III, and II/III were prepared by seeded emulsion polymerization. For these emulsions the relationship between polymer composition at the surface layer calculated from the A_m value and that in a particle calculated from the polymerization process was investigated. This relationship is remarkably affected by the order of polymerization, the hydrophilicity of polymer, the flexibility of the seed polymer, and the monomer addition method. The models of the morphology of these composite particles explain the results successfully.     

Thermodynamic data for divalent cations onto new modified glycidoxy silica surface at solid/liquid interface

Ethylenediamine molecule was chemically bonded on a silica gel surface previously anchored with 3-glycidoxypropyltrimethoxysilane. This new surface was employed to adsorb divalent cation from aqueous solutions at 298±1 K. The series of adsorption isotherms were adjusted to a modified Langmuir equation from data obtained by suspending the solid with MCl₂ (M=Cu, Ni, Zn and Co) solutions, which gave the maximum number of moles adsorbed as 1.54, 0.56, 0.45 and 0.36 mmol g^-1 for Cu, Ni, Co and Zn, respectively. Suspended aliquots of the chemically modified surface were calorimetrically titrated and the thermodynamic data showed the system is favored enthalpically and by free Gibbs energy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of inorganic electrolyte concentration on anionic-cationic adsorption films Part 1. Decylpyridinium chloride + sodium octylsulphonate + sodium chloride

The effect of NaCl on simultaneous adsorption of decylpyridinium chloride (R₁₀PyCl) and sodium octylsulphonate (R₈SO₃Na) on the free surface of their aqueous solutions has been examined. The surface excess of each component was determined on the basis of a suitable form of the Gibbs adsorption equation. The ionic strength effect on the adsorption of particular components of mixtures, as well as on the composition of anionic-cationic films adsorbed from equimolar solutions, is small. This is due to little difference in surface activity of surfactants investigated.     

Batch and semicontinuous emulsion copolymerization of vinyl acetate–butyl acrylate. II. Morphological and mechanical properties of copolymer latex films

Vinyl acetate/(VAc)-butyl acrylate/(BuA) copolymer latex films of various copolymer compositions were investigated for their morphological properties by electron microscopy techniques, and for their mechanical properties by dynamic mechanical spectroscopy (DMS), differential scanning calorimetry (DSC), and tensile strength measurements. Batch copolymer latex films showed domains of PBuA dispersed in PVAc matrix; the domain sizes were increased with increased BuA content. Semicontinuous latex films were homogeneous in composition. Glass transition temperatures T_g determined from DMS and DSC indicated the presence of two, low and high, transition temperatures for batch latex films. The two temperatures approached the individual homopolymers, with increased PBuA content up to 51 mol %. Semicontinuous latex films showed only one single T_g. Tensile properties of the batch copolymer films showed a higher ultimate tensile strength, higher Young's modulus, and lower percent elongation to break compared to semicontinuous latex films. These differences were found to reflect the effect of mode of monomer addition during the emulsion copolymerization process on the particle morphology, and confirmed earlier data on bulk, colloidal, and surface properties of the same copolymer latexes.     

Aggregation behavior and adsorption properties of salt-free catanionic surfactant mixtures containing tetradecyltrimethyl ammonium salts

The aggregation behavior of salt-free catanionic surfactants, tetradecyltrimethyl ammonium hydroxide (TTAOH)/fatty acid (FA) including octanoic acid (OA), decylic acid (DA) and lauric acid (LA) in aqueous solutions were studied. The critical micelle concentration(cmc), surface tension at cmc (γ_cmc), surface excess (Г_max), mean molecular surface area (A_min), adsorption efficiency (pc₂₀) and surface tension reduction effectiveness (π_cmc) were obtained from surface tension isotherms. The influence of temperature on the surface tension of salt-free TTAOH/FA (TTAOF) systems was investigated. Data of adsorption dynamics indicated that at fixed adsorption time, the order of adsorption capacity was TTAOH?相似文献   

Influence of size and functionality of polymeric nanoparticles on the adsorption behavior of sodium dodecyl sulfate as detected by isothermal titration calorimetry

Isothermal titration calorimetry was used to monitor the adsorption of the surfactant sodium dodecylsulfate (SDS) on different sized pure and carboxy functionalized polystyrene nanoparticles prepared by the mini-emulsion process. The ITC experiment gives, additionally to the CMC values, information about the interaction of the surfactant molecules to the particle’s surface due to the particle surface properties. The adsorption heat depends on the chemical composition of the polymer as well on the particle size. It also provides information about the surface coverage with surfactant and the number of additional adsorbed molecules per particle until full coverage by surfactant is obtained. The surfactant adsorption increases from 0.3 molecules per nm² for 50 nm to 8.5 molecules per nm² for carboxy functionalized particles with diameters larger than 160 nm. The area A _Surf-dens after the adsorption process gives information about the packing density of surfactant molecules on the particles in dependence of carboxy groups: an increasing number of carboxylic groups decreases the area occupied per SDS molecule. The adsorption process was also monitored by zeta potential measurements, where an increasing potential during the adsorption was detected.     

Adsorption behavior of water soluble polymers with lower critical solution temperature

The adsorption behavior of hydroxylpropyl cellulose (HPC), ethyl hydroxylethyl cellulose (EHEC) and poly-vinylalcohol (PVA) polymers, which have a lower critical solution temperature (LCST), have been studied in comparison with the behavior of hydroxylethyl cellulose (HEC) with no LCST. The saturated amount of adsorption (A _s ) for the polymers with LCST depended significantly on the adsorption temperature and theA _s , e. g., for HPC obtained at the LCST, the amount was 1.5 times as large as the value at room temperature. The highA _s values obtained at the LCST were maintained over a long period at room temperature, and the dense adsorption layer formed on the latex particles at the LCST showed a strong protective action against flocculation. Furthermore, the effect of the surface nature of the adsorbent on the polymer adsorption at the LCST has been investigated using six kinds of synthetic latices with different surface natures. It was found that the hydrophobic interaction between the polymer and the adsorbent plays an important role in inducing the adsorption, and the trend of increasing the hydrophilic character of the latex surface prevents the formation of the adsorption layer of the polymer.     

Adsorption of 1-pentanol on bismuth single-crystal plane electrodes

Cyclic voltammetry, impedance and chronocoulometry have been employed for the quantitative study of 1-pentanol (n-PenOH) adsorption at the bismuth single-crystal plane | aqueous Na₂SO₄ solution interface. The adsorption isotherms, Gibbs energies of adsorption ΔG _A ^∘, the limiting surface excess Γ_max and other adsorption parameters, dependent on the crystallographic structure of the electrodes, have been determined. The adsorption of n-PenOH on Bi single-crystal planes is mainly physical and is limited by the rate of diffusion of organic molecules to the electrode surface. Comparison of the adsorption data for n-PenOH with 1-propanol (n-PrOH), 1-butanol (n-BuOH), cyclohexanol (CH) and 1-hexanol (n-HexOH) shows that the adsorption characteristics depend on the structure of the hydrocarbon group. The adsorption activity of adsorbates at the bismuth | solution interface increases in the sequence n-PrOH < n-BuOH < CH ≤ n-PenOH < n-HA as the adsorption activity at the air | solution interface increases. For all the compounds studied, the adsorption activity increases in the sequence of planes (111)<(001)<(011ˉ). Received: 1 July 1998 / Accepted: 2 October 1998     

Effect of Organic Counterions on the Properties of N-Lauryl Diisopropanolamine Surfactants

The influence of counterions on the surface properties of N-lauryl diisopropanolamine surfactants is delineated using conductometry and surface tension measurements. Twelve types of organic counterions have been studied: C₁–C₁₂ monocarboxylic acids anions. The surface properties of the synthesized surfactants, including surface tension, critical micelle concentration (CMC), effectiveness (π_CMC), efficiency (pC₂₀), maximum surface excess (Γ_max), minimum surface area (A_min), Gibbs energy of micellization (ΔG_mic), and adsorption (ΔG_ad) processes in the aqueous. The biodegradability of the prepared surfactants was tested in river water using the die-away method. Petroleum-collecting and petroleum-dispersing capacities of the synthesized compounds on the surface of water of varying mineralization degree have been studied.     

Dynamic Behaviors and Morphology Change of Anionic Phospholipid DPPG Monolayer Caused by Bovine Serum Albumin at Air-Water Interface

The interaction between bovine serum albumin (BSA) and the anionic 1.2-dipalmitoyl-snglycero- 3-(phospho-rac-(1-glycerol)) (sodium salt) (DPPG) phospholipid at different subphase pH values was investigated at air-water interface through surface pressure measurements and atomic force microscopy (AFM) observation. By analyzing surface pressure-mean molecular area (π-A) isotherms, the limiting molecular area in the closed packing state-the concentration of BSA (A_lim-[BSA]) curves, the compressibility coefficient-surface pressure (C_S^-1-π) curves and the difference value of mean molecular area-the concentration of BSA (ΔA-[BSA]) curves, we obtained that the mean molecular area of DPPG monolayer became much larger when the concentration of BSA in the subphase increased at pH=3 and 5. But the isotherms had no significant change at different amount of BSA at pH=10. In addition, the amount of BSA molecules adsorbed onto the lipid monolayer reached a threshold value when [BSA]>5×10^-8 mol/L for all pHs. From the surface pressure-time (π-t) data, we obtained that desorption and adsorption processes occurred at pH=3, however, there was only desorption process occurring at pH=5 and 10. These results showed that the interaction mechanism between DPPG and BSA molecules was affected by the pH of subphase. BSA molecules were adsorbed onto the DPPG monolayers mainly through the hydrophobic interaction at pH=3 and 5, and the strength of hydrophobic interaction at pH=3 was stronger than the case of pH=5. At pH=10, a weaker hydrophobic interaction and a stronger electrostatic repulsion existed between DPPG and BSA molecules. AFM images revealed that the pH of subphase and [BSA] could affect the morphology features of the monolayers, which was consistent with these curves. The study provides an important experimental basis and theoretical support to understand the interaction between lipid and BSA at the air-water interface.     

Study on the interaction between anionic and cationic latex particles and Portland cement

The interaction between organic latex polymers and the surface of hydrating cement was investigated by measuring the zeta potential and adsorbed amount of polymer on cement. First, differently charged model latex particles were synthesized in aqueous media by well-known emulsion polymerization technique. The latex polymers were characterized by differential scanning calorimetry (DSC), dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM). Electrokinetic latex surface properties were investigated by means of streaming potential measurements using a particle charge detector (PCD). It is shown that the anionic latexes adsorb a considerable amount of Ca²⁺ from the cement pore solution. Next, adsorption of the latex polymers on the surface of hydrating cement was confirmed by zeta potential measurements using the electroacoustic method. A water to cement ratio in the cement paste as low as 0.5 was studied, representing actual conditions in mortar and concrete. Additionally, adsorption isotherms were determined in a sedimentation test using the depletion method. For all latex polymers, Langmuir type adsorption isotherms were found. The latex dosages required to achieve saturated adsorption on the cement surface obtained from zeta potential measurements correspond well with those determined in the sedimentation test. Electron microscopy photographs confirm that the charged latex polymers adsorb selectively on surface areas of hydrating cement showing opposite charge. This way, domains of organic latex polymers exist on the cement surface. They provide adhesion between the inorganic cement matrix and the organic polymer film formed later on by particle coalescence as a result of cement hydration and drying.     

Kinetics and equilibrium of adsorption on 4A zeolite

Adsorption isotherms for Ar, 0₂, N₂, CO, CO₂, CH₄, and C₂H₆ on 4A zeolite at three or more temperatures were determined. An adsorption equation based on a 2-dimensional virial equation in terms of integer powers of the reciprocal of (A - σ) was shown to fit the equilibrium data accurately with three constants for C₂H₆ and two constants for other gases. Here A is the area per molecule and σ is the area of the molecule in a close-packed situation.Rates of adsorption and desorption of Ar, N₂, CO, CH₄, and C₂H₆ on 4A zeolite were determined over ranges of temperature in which the rate was moderately fast. Electron microscopy showed that the particles were cubes, and their size-distribution was determined. The conventional Fick's law rate equation for cubes was used to produce a generalized rate curve for the particle size distribution of the adsorbent. This curve was applied to the last 20% of the rate curve to obtain a diffusivity that could be related to the final amount adsorbed. This procedure also avoids the initial rapid portion of the adsorption, in which large variations of adsorbent temperature from that of the bath often occur.The diffusivities increased with amount adsorbed by a small extent for Ar and CH₄ and by larger amounts for N₂, CO, and C₂H₆. The activation energy for diffusion, as well as the heat of adsorption, were nearly independent of amount adsorbed for Ar and CH₄, but these quantities decreased substantially with coverage for N₂, CO, and C₂H₆. The dependence upon amount adsorbed of diffusivity and activation energy seemed related to the shape of the adsorption isotherm; those for Ar and CH₄ were nearly linear, whereas isotherms for the other gases had large curvatures. The activation energy for diffusion varied with coverage in the same way as heat of adsorption.     

不同水煤浆分散剂与煤之间的相互作用规律研究: Ⅹ 分散剂在煤粒表面上的吸附作用特征

研究了6种水煤浆分散剂在14种不同变质程度煤上的吸附作用特征。结果表明，多数分散剂在煤粒表面达到单层饱和吸附后，又形成多层吸附，单层饱和吸附量与煤的变质程度、比表面积以及分散剂的性质有关。在相同粒度分布下，煤的变质程度越低，表面含氧亲水官能团的比例越高，孔隙率越高，比表面积越大，这对增大吸附量有利。煤的变质程度越高，其表面疏水区面积的比例越高，分散剂通过疏水基团紧密吸附在煤表面的比例越大，这对增加高阶煤的吸附量有利。对不同煤，是变质程度还是比表面积为吸附分散剂的主控因素，主要依赖于分散剂的结构与性质。对同种煤，疏水与亲水基团呈线型分立分布的分散剂，吸附量明显高；而疏水与亲水基团呈线型间隔分布的分散剂，吸附量明显小。     

Polymerization of vinyl acetate in aqueous media. Part IV. Influence of preformed (“seed”) latex upon polymerization kinetics and particle size

The polymerization of aqueous solutions of vinyl acetate initiated by K₂S₂O₈, has been studied in the presence of different concentrations of a fine “seed” latex, both in the absence and in the presence of a surfactant (sodium hexadecyl sulfate). Both kinetics and final latex size were measured, the latter showing whether fresh nucleation had occurred or not. The results suggest that surfactant adsorbed on the latex surface greatly influences the capture, by the latex surface, of oligomers formed in the aqueous phase and this, in turn, markedly affects both nucleation and kinetics. The number of free radicals per particle does not appear to be constant even with the finest particles used (ca. 50 mμ).