Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from <Emphasis Type="Italic">N</Emphasis>-Methylol Acrylamide

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N‐methylol acrylamide using a two‐step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self‐assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02–0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.     

Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives

Work was performed to distinguish the role of sulfonate (–SO₃ ^?) and sulfate (–OSO₃ ^?) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants [sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra-n-pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l-ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).     

Synergetic effect of chelating agent and nonionic surfactant for benzotriazoleremoval on post Cu-CMP cleaning

The cleaning of copper interconnects after chemical mechanical planarization (CMP) process is a critical step in integrated circuits (ICs) fabrication. Benzotriazole (BTA), which is used as corrosion inhibitor in the copper CMP slurry, is the primary source for the formation of organic contaminants. The presence of BTA can degrade the electrical properties and reliability of ICs which needs to be removed by using an effective cleaning solution. In this paper, an alkaline cleaning solution was proposed. The alkaline cleaning solution studied in this work consists of a chelating agent and a nonionic surfactant. The removal of BTA was characterized by contact angle measurements and potentiodynamic polarization studies. The cleaning properties of the proposed cleaning solution on a 300 mm copper patterned wafer were also quantified, total defect counts after cleaning was studied, scanning electron microscopy (SEM) review was used to identify types of BTA to confirm the ability of cleaning solution for BTA removal. All the results reveal that the chelating agent can effectively remove the BTA residual, nonionic surfactant can further improve the performance.     

Synthesis and surface activity of nonionic surfactants containing fluorocarbon hydrophobes

Nonionic surfactants having polydisperse polyoxyethylene chains and highly fluorinated hydrophobes were synthesized via a complex reaction route and their adsorption at water/air interfaces studied. They exhibit high surface activity and decrease both effectively and efficiently the surface tension of their aqueous solutions. The effect of the length of the polyoxyethylene chain upon surfactant surface activity is relatively low. Lower values of surface tension, below 30 mN m^?1, are obtained for surfactants having a low degree of ethoxylation. Surfactants having two terminal highly fluorinated hydrophobes are less surface active than analogues with one terminal hydrophobe.     

Analysis of nonionic surfactants in bench-scale biotreater samples

The effluents and activated sludges used in benchscale biotreater units have been analyzed for nonionic alcohol ethoxylates and their residues. Separate bench-scale units were fed linear alcohol ethoxylates (AE), highly branched and branched nonylphenol ethoxylates. Effluents and sludges were first pretreated by a foam sublation technique to provide a gross separation of surfactants from the environmental matrix. This step was followed by normal-phase high-performance liquid chromatography (HPLC) with either fluorescence detection (FD) or evaporative light-scattering detection (ESLD). The AEs were derivatized with phenylisocyanate and analyzed by normal-phase HPLC coupled with FD. At extremely low surfactant levels, pretreatment of large sample volumes resulted in interferences on derivatization. Hence, a normal-phase HPLC method with ELSD was developed. Although some interferences do appear using ELSD, this method appears to be a more viable alternative to derivatization/FD for very low levels of AE. HPLC with FD and ELSD detection methods are more quantitative and provide information on the polyoxyethylene chain than is possible with traditional methods like cobalt-thiocyanate active substance. Presented at the 82nd AOCS Annual Meeting & Expo, May 1991, Chicago, Illinois.     

IN-SITU REDUCTION OF A METHANOL SYNTHESIS CATALYST IN A THREE-PHASE SLURRY REACTOR

ABSTRACT

A new method for the reduction of metal oxide catalysts has been developed, for the reduction of the CuO - ZnO - A1203 catalyst for liquid phase methanol synthesis. The reducing agent is a 5% hydrogen in nitrogen mixture and the operation is carried out at 446.09 KPa. This method makes it possible to reduce finely crushed catalyst (-100 + 120 mesh) in a three phase slurry reactor. This method offers several advantages over methods in which the catalyst is reduced in a gas-solid contact mode and then slurried for use. The catalyst has been shown to be very effectively reduced and reaches its full production capacity after reduction.     

重防腐涂料用水性环氧乳液的制备

采用固体双酚A型环氧树脂与高分子量聚醚反应合成水性环氧树脂专用非离子型乳化剂,然后结合相反转技术制备水性环氧乳液。讨论了催化剂三氟化硼乙醚(BF3-乙醚)的用量对环氧树脂CYD011和聚乙二醇PEG6000反应体系环氧值的影响,并利用红外光谱和凝胶渗透色谱对合成乳化剂的结构进行表征,探讨了环氧树脂与PEG6000的摩尔比、乳化剂质量分数、乳化温度及不同分子量的环氧树脂对乳液性能的影响。结果表明,当环氧树脂的环氧当量为450～500,乳化温度为75℃、催化剂用量为0.40%、n(环氧树脂)∶n(PEG6000)=1∶1、乳化剂质量分数为15%时,所制得的水性环氧乳液粒径小于1μm,稳定性高。由此乳液制备的涂料涂膜柔韧性为1mm,冲击强度为50kg·cm,浸泡在质量分数为5%的NaCl溶液中17d完好,耐盐雾480h完好。该乳液可应用于重防腐涂料。     

Application of Oil/Water Nanoemulsions as a New Alternative to Demulsify Crude Oil

Oil-in-water nanoemulsions were developed and evaluated for effectiveness in breaking down crude oil emulsions. The nanoemulsions were prepared using two types of ethoxylated nonionic surfactants: nonylphenol and lauryl ether, at a concentration of 12 wt%, and the solvent xylene as the oil phase, at different concentrations (5, 7, and 10 wt%). The results of the demulsification tests showed that the nanoemulsions developed are a viable alternative to break down petroleum emulsions, with efficiency ranging from 90 to 95%. Also, the greater the xylene concentration in the nanoemulsion, the faster the demulsification process was.     

Modification to the renneting functionality of casein micelles caused by nonionic surfactants

Nonionic emulsifiers of small molecular weight such as polysorbates are widely used in dairy products. Nevertheless, the mechanism of interaction between these surfactants and milk proteins is not yet fully understood. This work investigated the effect of Tween 20 on casein micelles by studying the renneting behavior of skim milk in the presence of different amounts of surfactant. The presence of Tween accelerated both the first and second phase of renneting in skim milk. The gel obtained showed a higher elastic modulus than that of a skim milk gel, but also showed similar brittleness. By varying the size of the surfactant (Tween 20 or Tween 80) as well as the colloidal state of the proteins in solution, it was possible to demonstrate that the surfactant did not have a direct effect on the activity of the enzyme, but rather had a direct effect on the casein micelles. The effect of surfactant on the gelation point was reduced by increasing surfactant size. The presence of Tween caused an increase in the size of the micelles without affecting their stability. In addition, Tween did not alter the amount of caseins free in the serum phase. These findings can contribute to improving our ability to custom design final structures in rennet-induced gels, though further studies are needed to fully understand the mechanism at play when casein micelles are enzymatically cleaved in the presence of nonionic surfactants of small molecular weight.     

非离子表面活性剂对超临界CO2下酶催化蛋白质水解的影响

研究了在超临界CO2介质中非离子表面活性剂对胰酶催化牛血清白蛋白(BSA)水解的影响,通过系统水含量及系统压力的变化来分析四种非离子表面活性剂平平加O、十三烷基醇聚氧乙烯醚(1380)、聚乙二醇辛基苯基醚(OP-10)及Tween 80对胰酶催化牛血清白蛋白水解的影响,并用SDS-PAGE凝胶电泳法及分析软件TotalLab对蛋白质的水解度进行分析。研究表明,非离子表面活性剂在低系统压力及低系统水含量下能促进胰酶催化牛血清白蛋白水解,使水解率提高20%以上,且水解率随着系统压力的升高而上升,随着系统含水量的升高而下降。当系统水含量达到30μL以上时,非离子表面活性剂对胰酶催化牛血清白蛋白水解的影响不明显。