表面活性剂对驱油聚合物界面剪切流变性质的影响

利用双锥法研究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)对油田现场用部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液的界面剪切流变性质的影响,实验结果表明:HMPAM分子通过疏水作用形成界面网络结构,界面剪切复合模量明显高于PHPAM.SDBS和CTAB通过疏水相互作用与HMPAM分子中的疏水嵌段形成聚集体,破坏界面网络结构,剪切模量随表面活性剂浓度增大明显降低.同时,界面膜从粘性膜向弹性膜转变.低SDBS浓度时,少量SDBS分子与PHPAM形成混合吸附膜,界面膜强度略有升高;SDBS浓度较高时,界面层中PHPAM分子被顶替,吸附膜强度开始减弱.阳离子表面活性剂CTAB通过静电相互作用中和PHPAM分子的负电性,造成聚合物链的部分卷曲,从而降低界面膜强度.弛豫实验结果证实了表面活性剂破坏HMPAM网络结构的机理.     

不同结构驱油聚合物的界面剪切流变性质

利用双锥法研究了油田现场用超高分子量部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液与航空煤油间的界面剪切流变性质,考察了时间、应变幅度和剪切频率对不同浓度PHPAM和HMPAM溶液界面剪切流变参数的影响.结果表明,只有在适宜的剪切频率条件下,流变数据才能反映界面膜的结构信息.HMPAM分子具有界面活性,能吸附在界面上,其界面膜的强度随时间变化逐渐增强,且在高浓度时以黏性为主;PHPAM分子不具有界面活性,其剪切流变参数没有时间依赖性,界面层以弹性为主.HMPAM能通过疏水作用形成界面网络结构,界面膜的剪切复合模量明显高于PHPAM界面层.HMPAM界面层中网络结构在剪切形变作用下的破坏与重组这一慢弛豫过程是其强度较高的原因.     

驱油体系化学剂间相互作用对界面吸附膜的影响

采用界面张力弛豫技术研究了不对称Gemini表面活性剂C12COONa-p-C9SO3Na、部分水解聚丙烯酰胺Mo-4000、疏水缔合水溶性聚丙烯酰胺(HMPAM)等驱油体系化学剂在癸烷/水界面上的扩张流变性质,考察了不同离子强度、不同类型电解质对体系界面流变性质的影响,计算得到界面扩张弹性模量和粘性模量的全频率谱,并通过归一化方法(cole-cole图)探讨了界面吸附膜的弛豫过程。研究发现,界面膜内分子重排和界面与体相间分子扩散交换是影响膜性质的主要弛豫过程。表面活性剂体相浓度增大有利于界面分子重排过程,而低频有利于扩散交换过程;不同结构聚合物以及不同离子强度、不同类型电解质对表面活性剂吸附膜有不同的影响。     

Gemini表面活性剂对疏水缔合聚丙烯酰胺界面吸附膜扩张流变性质的影响

采用小幅低频振荡和界面张力弛豫技术, 考察了疏水缔合水溶性聚丙烯酰胺(HMPAM)在正癸烷-水界面上的扩张黏弹性质, 研究了不对称Gemini表面活性剂C₁₂COONa-p-C₉SO₃Na对其界面扩张性质的影响. 研究发现, 疏水链段的存在, 使HMPAM在界面层中具有较快的弛豫过程, 扩张弹性显示出明显的频率依赖性. 表面活性剂分子可以通过疏水相互作用与聚合物的疏水嵌段在界面上形成类似于混合胶束的特殊聚集体. 表面活性剂分子与界面聚集体之间存在快速交换过程, 可以大大降低聚合物的扩张弹性. 同时, 聚合物分子链能够削弱表面活性剂分子长烷基链之间的强相互作用, 导致混合吸附膜的扩张弹性远低于单独表面活性剂吸附膜.     

聚醚类破乳剂的界面扩张流变性质

采用悬挂滴方法研究了不同结构聚醚类破乳剂与煤油间的界面张力及界面扩张流变性质. 结果表明, 4种聚醚类破乳剂均具有较强的降低界面张力能力, 且支链化程度越低分子在界面上排列越紧密, 直线型破乳剂在低浓度条件下界面张力最低. 破乳剂的分子尺寸较大, 慢弛豫过程控制界面膜性质, 吸附膜以弹性为主. 同时, 柔性聚氧乙烯链和聚氧丙烯链对界面膜性质的影响较大, 随着支链化程度增大, 界面分子间相互作用增强, 界面膜弹性增强, 黏性降低.     

疏水改性聚丙烯酰胺的荧光研究

使用荧光探针技术,跟踪了疏水改性聚丙烯酰胺(HMPAM)在溶液中的变化过程,对HMPAM在溶液中的聚集行为进行了研究。同时也对部分水解聚丙烯酰胺(HPAM)作了对比研究。发现HMPAM在溶液中具有独特的变化规律:由疏水缔合形成超分子聚集体,再由超分子聚集体形成布满整个溶液空间网络结构的过程。并使用粘度法对其宏观流变性能进行了研究,发现两种手段所得的结果具有较好的对应关系。     

表面活性剂与聚丙烯酰胺在油水界面的流变性

界面流变学是研究界面膜在外力作用下流动与形变的科学，界面粘度是油水界面膜的一种重要性质，它的大小与成股分子排列的紧密程度、成膜分子相互作用力的大小和是否有结构形成有关［‘1，人们早就对表面流变性质进行了相当系统而深入的研究［’41，但是有关油水界面流变性质的     

聚丙烯酰胺对烷基苯磺酸盐界面吸附膜扩张流变性质的影响

采用小幅低频振荡和界面张力弛豫技术, 研究了部分水解聚丙烯酰胺(Mo-4000)和阴离子表面活性剂2-丙基-4,5-二庚基苯磺酸钠(377)体系在癸烷/水界面上的扩张黏弹性质, 并考察了电解质对体系界面流变性质的影响. 研究结果发现, 低表面活性剂浓度时, 聚合物的加入大大降低了扩张模量; 而高表面活性剂浓度时, 聚合物的存在导致了界面膜更接近弹性膜. 一方面电解质压缩双电层, 增加界面膜的紧密程度, 造成高频条件下扩张模量增大; 另一方面, 电解质增强表面活性剂分子在界面与体相间的扩散交换作用, 增大了扩张模量的频率依赖性, 造成低频条件下扩张模量降低.     

短链烷基对多取代烷基苯磺酸盐界面性质的影响

利用悬挂滴方法研究了2,5-二乙基-4-壬基苯磺酸钠(292)、2,5-二丙基-4-壬基苯磺酸钠(393)和2,5-二丁基-4-壬基苯磺酸钠(494)在空气-水表面和正癸烷-水界面的扩张流变性质,考察了时间、界面压、工作频率及体相浓度对扩张弹性和粘性的影响。研究发现,在低表面活性剂浓度条件下,表面吸附膜类似弹性膜,其强度由膜内分子的相互作用决定;高浓度下体相与表面间的扩散交换过程控制表面膜的性质。油分子的插入导致界面吸附分子之间相互作用的削弱,扩散交换过程主导界面膜性质;但随着短链烷基长度增加,油分子的影响变小。表面膜的强度在吸附达到平衡前已经决定,而界面膜在吸附饱和后仍然随界面分子重排而变化。     

不同结构烷基苯磺酸盐油水界面扩张粘弹性质

研究了2-甲基-5-(1-庚基辛基)苯磺酸钠、辛基苯磺酸钠和十六烷基苯磺酸钠在正辛烷-水界面上的扩张粘弹性质, 考察了链长变化和疏水基支链化对分子界面行为的影响. 研究结果表明, 链长增加导致分子间相互作用增强, 弹性增大; 疏水支链在界面上可能由于缠绕和变形产生界面慢弛豫过程, 导致较高的扩张模量.     

Interfacial Dilational Properties of Hydrophobically Modified Partly Hydrolyzed Polyacrylamide and Anionic Surfactants at the Water-Decane Interface

The dilational viscoelastic properties of hydrophobically modified partly hydrolyzed polyacrylamide and anionic surfactants (4,5-diheptyl-2-propylbenzene sulfonate and gemini surfactant C₁₂COONa-p-C₉SO₃Na) in the absence or presence of electrolyte have been investigated at the decane–water interface by means of longitudinal method and the interfacial tension relaxation method. Experimental results show that at low surfactant concentration, the increase of the dilational modulus by the addition of surfactant molecules at low frequency might be explained by the mix-adsorption of the polymer chains and surfactant molecules. At the same time, polymer chain could sharply decrease the dilational modulus of surfactant film mainly due to the weakening of the strong interactions among long alkyl chains in surfactant molecules. At high surfactant concentration, the addition of surfactant molecules can decrease the dilational modulus of polymer solution due to the fast process involving in the exchange of surfactant molecules between the interface and the mixed complex formed by surfactant molecules and hydrophobic micro-domains. The added electrolyte, which results in screening of electrostatic interactions between the ionized groups, generally increases the frequency dependence of the interfacial dilational modulus. The data obtained on the relaxation processes via interfacial tension relaxation measurements can explain the results from oscillating barriers measurements very well.     

疏水链长对聚氧乙烯失水山梨醇脂肪酸酯界面扩张流变性质的影响

利用悬挂滴方法研究了系列聚氧乙烯失水山梨醇脂肪酸酯(TweenX)在正癸烷-水界面的扩张流变性质. 实验结果表明, 疏水烷基链长较短的Tween20 分子在界面上吸附量较大, 分子排列更紧密, Tween40 和Tween60具有大致相同的“有效截面积”, 导致饱和吸附时界面张力(γ_cmc)比较接近. TweenX浓度大于临界胶束浓度(cmc)时, 由于Tween20 分子排列的更加紧密, 模量和弹性大于Tween40 和Tween60. 当TweenX的疏水烷基链长达到一定长度时, TweenX的界面膜性质受疏水链长的影响减弱, Tween40和Tween60的扩张参数相差不大.     

疏水基支链化对甜菜碱表面扩张流变性质的影响

利用悬挂滴方法研究了同分异构的直链（C₁₆PB）和支链（C₁₆GPB）十六烷基羟丙基羧酸甜菜碱的表面扩张流变性质,考察了时间、表面压、工作频率及体相浓度对扩张模量和相角的影响.研究发现,羟丙基甜菜碱分子在溶液表面上吸附时,整个亲水基团倾向于平铺在表面上,造成较高的表面扩张模量,表面膜性质由亲水基团取向变化等膜内过程控制.甜菜碱分子疏水烷基的支链化造成分子间相互作用增强,不仅能增大模量,而且在高浓度条件下出现动态模量的最大值现象,说明表面膜的强度与分子排布密切相关,并非单纯由表面分子浓度决定.     

Influence of Oleic Acid and Electrolyte on the Interfacial Dilational Properties of Surfactant/Polymer Systems at the Decane-Water Interface

The dilational properties of partly hydrolyzed polyacrylamide (HPAM) and 4,5-diheptyl-2-propylbenzene sulfonate (377) mixed systems in the absence or presence of electrolyte or oleic acid at the oil-water interface have been described by means of the oscillating barriers method and the interfacial tension relaxation method. The polymer plays different roles in influencing the nature of polymer-surfactant adsorbed layers at different surfactant concentrations. At low surfactant concentration, the addition of polymer perhaps weakens the “entanglement” of long alkyl chains, which decreases strikingly the dilational modulus of the adsorbed layer. At high surfactant concentration, the addition of the polymer increases the dilational modulus due to the hydrophobic interactions between polymer and surfactant molecules. On the case of adding electrolyte, the frequency dependence of dilational modulus increases due to the enhancement of exchange process of surfactant molecules and bivalent cation has more obvious effect than Na ion. Oleic acid plays dual roles in controlling interfacial dilational properties of mixed adsorption films: a small quantity of oleic acid increases the dilational modulus by forming densely packed mixed adsorption layer with surfactant molecules, while the superfluous addition of oleic acid could decrease the dilational modulus mainly due to the weakening of the “entanglement” among long alkyl chains in surfactant molecules.     

Dilational properties of gemini surfactant/polymer systems at the air–water surface

The surface properties of mixed system containing gemini anionic surfactant 1,2,3,4-butanetetracarboxylic sodium, 2,3-didodecyl ester and partly hydrolyzed polyacrylamide were investigated by surface tension measurements and oscillating bubble methods. The influences of surfactant concentration, dilational frequency, temperature, pH, as well as salts on dilational modulus were explored. Meanwhile, the interfacial tension relaxation method was employed to obtain the characteristic time of surface relaxation process. The polymers play important roles in changing the interfacial properties especially at lower surfactant concentration. The possible mechanism of the polymer in changing the interfacial properties is proposed. Both the hydrophobic and electrostatic interaction among the surfactants and polymers dominate the surface properties of mixed system. These dynamic properties are of fundamental interest in understanding the structure of adsorption layers, dynamics of surfactant molecules, and their interaction with polymers at the surface.     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.     

Effect of Demulsifier Structures on the Interfacial Dilational Properties of Oil–Water Films

The dilational properties of a branch-shaped polyether-type nonionic demulsifier (PEB), a comb-shaped polyether-type nonionic demulsifier (PEC), and a star-shaped polyether-type nonionic demulsifier (PES) at the decane–water interfaces were investigated by Langmuir trough method through oscillating barrier and interfacial tension relaxation methods, which are mainly in the influences of oscillating frequency and bulk concentration on dilational properties. Meanwhile, the effect of demulsifiers on interfacial dilational modulus of diluted crude oil was also explored. The experimental results indicate that all demulsifiers can decrease the dilational modulus of diluted crude oil at the experimental concentration. The addition of PEB causes the dilational modulus of crude oil to be lower than that at the water–decane interface. The demulsifier PEC has a similar effect with PES to influence the interfacial film of crude oil: at low concentration, the dilational modulus of mixed interfacial film is lower than that of demulsifier alone, while at high concentration, the dilational modulus of mixed interfacial film is slightly higher than that of demulsifier alone. The dependence of static modulus on the bulk concentration is consistent with the trend of interfacial dilational modulus with concentration for demulsifiers PEB, PEC, and PES. The studies about the structure modulus show that the new demulsifiers PEC and PES have a stronger ability than branch-shaped demulsifier PEB to destroy the interfacial film.