Yield stress and viscoelastic properties of high internal phase ratio emulsions

 The rheology of high internal phase ratio oil-in-water emulsions was investigated using a controlled-stress rheometer. The dispersed-phase (oil) concentration was varied from 71.24 to 89.61% by volume. Three different types of rheological experiments were conducted for each emulsion, namely: steady shear, oscillatory shear, and creep/recovery experiments. All the emulsions investigated in this study possess a yield stress. The yield-stress values obtained from different rheological experiments for the same emulsion show good agreement with each other. The yield-stress value increases exponentially with an increase in the dispersed-phase concentration. The yield-stress data of this study can be described quite well with the Princen and Kiss equation for high internal phase ratio emulsions provided that the thickness of the interdroplet films is taken into account. For any given emulsion, the storage modulus, measured in the linear viscoelastic region, is found to be constant, independent of the frequency, indicating a solid-like behaviour. The value of the storage modulus increases with an increase in the dispersed-phase concentration. The storage modulus data are interpreted in terms of the Princen and Kiss equation. Received: 23 October 1998 Accepted in revised form: 18 February 1999     

Rheological characterization of polysaccharide-surfactant matrices for cosmetic O/W emulsions

Rheometrical techniques can be profitably used for polysaccharide matrices in order to evaluate their suitability for the preparation of stable cosmetic O/W emulsions. In particular, the rheological properties of aqueous scleroglucan systems were investigated under continuous and oscillatory shear conditions in a polymer concentration range (0.2-1.2% w/w) embracing the sol/gel transition. The effects due to the addition of two different surfactants (up to 10% w/w) were examined at constant polymer concentration (0.4% w/w). The selected additives are a nonionic polymeric siliconic surfactant (dimethicone copolyol) and a cationic surfactant (tetradecyltrimethylammonium bromide), respectively. Polysaccharide-surfactant interactions leading to complex formation were detected also through rheology. The combined action of both nonionic and cationic surfactants in the polymer solution was examined at two different surfactant concentration levels (5 and 10% w/w), demonstrating the beneficial effects produced on the mechanical properties of the polymer matrix by the coexistence of both surfactants. Such beneficial effects are confirmed by the stability and rheology shown by the emulsions prepared. In this way, the results point out the good agreement between the rheology of the continuous phase and the final characteristics of the emulsion obtained.     

Rheology of viscoelastic anionic micellar solutions in the presence of a multivalent counterions

The growth and structure of anionic micelles sodium dodecyl trioxyethylene sulfate (SDES) in the presence of a multivalent counter-ion, Al³⁺, were investigated by means of rheological methods and the technique of freeze-fracture transmission electron microscopy. It was found that wormlike micelles and network structures could be formed in SDES/AlCl₃ aqueous micellar solutions, according to the measurements of the zero-shear viscosity, the complex viscosity and the dynamic moduli (storage modulus and loss modulus), and the application of the Cox–Merz rule and a Cole–Cole plot. The cyclic shear test, the plateau modulus and the relaxation time were also studied to express the rheological properties of the wormlike micellar solutions. The structure was of a character of a nonlinear viscoelastic fluid and departed from the simple Maxwell model. Received: 23 November/2000 Accepted: 31 January 2001     

Aeration of emulsions by whipping

During aeration of food emulsions such as dairy cream and ice cream, small gas bubbles are introduced, which are often stabilized by a layer of adsorbed emulsion droplets. It is shown that the maximum achievable volume of gas bubbles that can be incorporated by whipping depends on the effectiveness of the introduction of gas during the first stage of whipping and is furthermore limited by packing constraints. The main factors relevant for the latter limitation are the thickness of the coating of emulsion droplets at the bubble surface, the ratio between the droplet and bubble radii, and the fat content of the emulsion. It is hypothesized that, during whipping, a dynamic process of bubble break-up and coalescence adjusts the average bubble size and the volume of gas incorporated in the foam to the constraint of close packing of the bubbles. The consequences of this mechanism for whipping of emulsions are discussed.     

Factors affecting the stability of foamed concentrated emulsions

This paper attempts to quantify the stability of three-phase systems generated by aerating concentrated water-in-oil emulsions. In such materials, which we call foamed emulsions, the continuous phase is itself a two-phase system. In this work, we modify and extend the method originally proposed by Iglesias et al. (Colloids and Surfaces A, 98 (1995) 167–174) to viscous three-phase foams. The modified method involves imparting a destabilising force to the sample to make the foam short-lived and measuring the change in height as a function of decay time. The change of height during decay represents the rate at which gas is evolved from the foamed emulsion and is logarithmic with time. The data treatment yields two values, the decay constant and half-life, which are used as a means of measuring and comparing stability. Two distinct decay mechanisms (smooth decay and catastrophic collapse) operate in foamed emulsions that are subjected to oscillations. For a given decay mechanism, the decay constant is an intrinsic property of the foamed emulsion and is independent of the imposed oscillations. Experimental results indicate that different bubble stabilising surfactants and emulsion morphology significantly affect the foam stability, and that the stability is inversely related to the initial expansion. Examination of the gas–emulsion interface shows a segregation of droplets, with smaller droplets found preferentially at the gas–emulsion interface.     

填充聚合物的熔体流变学

颗粒填充聚合物（包括聚合物纳米复合材料）溶体通常表现出模量升高、频率依赖性的改变以及高含量填充体系的屈服行为等与单纯聚合物明显不同的流变行为,并且这些流变特性还会受到填料含量、形状尺寸以及颗粒-聚合物之间相互作用等诸多因素的影响。填充聚合物的宏观流变行为是与其微观结构的形成和演化以及高分子链在特定条件下的阻尼松弛过程密切联系在一起的。本文综述了颗粒填充聚合物（包括聚合物纳米复合材料）在力场作用下的流变性以及各种因素对其流变行为的影响,尤其是着重阐述了聚合物纳米复合材料的流变松弛机理和基于热力学理论建立起来的、描述填充体系熔体流变行为的Leonov模型。     

Study of the interfacial tension in model and technical emulsions in the presence of surfactants and inorganic electrolytes

Interfacial tension in the oil/water system in the presence of various ionic surfactants and inorganic electrolytes was studied. Special features of the effect of the surfactant and oil phase natures, of the structure of their molecules, and also of the electrolytes containing ions with various radii, valences, and hydratabilities on the value of the interfacial tension were studied. The criteria and conditions of obtaining model emulsions based on paraffin hydrocarbons and technical emulsions based on vegetable oils were determined.     

We the droplets: A constitutional approach to active and self-propelled emulsions

The field of active matter, and particularly active emulsions, is growing rapidly, with significant progress made recently on both theoretical and experimental fronts. Here, we summarize experimental research progress related to active droplets. The constitution of active droplets, in particular the chemical compositions and structure of interfaces, is critical. We discuss how emulsion properties such as mechanism of motion, speed, trajectory, interaction strength, and lifetime are related to the droplet composition. We consider not only traditional single emulsions but also more complex variants, such as Janus droplets, Pickering emulsions, and multiple emulsions. Active behavior of isolated droplets as well as pairwise and multibody interactions between droplets is described. The influence of physical barriers that shape the local chemical gradients and fluid flow is also highlighted. This review provides perspective on the past, current, and promising future experimental research directions in active droplet research.     

Stabilisation of emulsions by interfacial polymerisation of poloxamer surfactant derivatives

A method of increasing the stability ofo/w emulsions and providing a potential additional barrier to drug release from the oil droplets is described. Diacryloyl derivatives of non-ionic block copolymers (poloxamers) have been used to stabilise isopropyl myristate in water emulsions. Cross-linking of these stabilisers at the oil-water interface produces a polymeric region which increases the stabilityo/w emulsions to centrifugation and of thew/o emulsions to creaming.     

磁流变体流变学特性研究

对所研制的矿物油介质和硅油介质磁流变体样品的零场粘度、磁流变性能、示功及速度特性进行了系统的测试和分析,并对其影响因素进行了详细的讨论.研制的磁流变体零场粘度小于0.5 Pa s(γ=81 s-1)且具有良好的粘温特性; 磁流变体的剪切应力接近和超过70 kPa(B=6000 Gs); 在智能减振器的应用试验中获得理想的示功特性曲线.     

动态流变学对PVDF/PTW共混物流体相容性研究

采用熔融共混法制备了聚偏氟乙烯/乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PVDF/PTW)共混物,利用流变仪考察了PVDF/PTW共混物的相互作用及两者的相容性.观察共混物在200℃下的流变曲线,发现在低频区,共混物中PTW含量越大,共混物的流变曲线越偏离经典流变理论,这个结果与cole-cole图相一致.通过时温叠加原理(时温等效主曲线、Han曲线和v GP曲线)系统研究了不同组成的PVDF/PTW共混体系在均相区和相分离区的黏弹行为.结果表明,在均相区,不同温度下,共混体系的动态模量利用时温叠加原理,通过水平位移就可以很好地叠加在一起,无论是储能模量还是损耗模量,在低频末端均近似地符合经典低频末端标度关系;在相分离区,动态模量偏离了经典的低频末端标度关系,其中储能模量的偏离尤为明显,从而导致了时温叠加原理的失效,相应的Han图、v GP图也表现出不同于均相体系的特征,这些特征的响应可以用来表征共混体系的相容性,表明在研究的一系列配比(PVDF/PTW 100/0、90/10、70/30、50/50、30/70、10/90、0/100,W/W)中,当PVDF/PTW=90/10(W/W)时,两者的相容性较好.SEM也证实了这个结论.     

The determination of interfacial tension by differential capillary rise

A method for directly determining interfacial tension without iteration from the difference in height between two capillaries is presented. An experimental technique is described for organic liquids both lighter and heavier than water, in which the menisci recede over surfaces wetted by the aqueous phase, thus providing the most favourable conditions for zero contact angle. The values determined experimentally using tables prepared from the known shapes of sessile interfaces agree well with accepted values of the interfacial tension.     

Syneresis of Carrageenan Gels: NMR and Rheology

Abstract

A novel and quick method to predict the syneresis of carrageenan gels using ¹³³Cs NMR is proposed. Cesium ions in carrageenan undergo a sharp change in mobility while cooling. By correlating that to the mobility of the polymer chains, we can identify a transition from a mobile gel to a frozen “glassy state” as a function of temperature and ion concentration. The demarcation between gel and glass distinguishes between systems that synerese over long times and those that do not. This is supported by rheological measurements that show that the modulus remains constant over time at temperatures below the transition temperature.     

Synthesis of star polymeric ionic liquids and use as the stabilizers for high internal phase emulsions

A series of well-defined core cross-linked star (CCS) polymeric ionic liquids (PILs) were synthesized via a three-step approach. First, the styrenic imidazole-based CCS polymer (S-PVBnIm) was prepared by the RAFT-mediated heterogeneous polymerization in a water/ethanol solution, followed by the quaternization of S-PVBnIm with bromoalkanes and anion exchange. The CCS polymers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained CCS polymers were used as the effective emulsifiers for oil-in-water high internal phase emulsions (HIPEs). Multiple oils with different polarity including n-dodecane, undecanol, toluene and octanol were emulsified using 0.5 wt% S-PVBnIm aqueous solution under the acidic condition to form HIPEs with long-term stabilities. The excellent emulsification properties of CCS PILs were demonstrated by HIPE formation for a variety of oils. The properties of HIPEs in terms of emulsion type and oil droplet size were characterized by the confocal laser scanning microscopy (CLSM). The intriguing capability of CCS PILs to stabilize HIPEs of various oils holds great potentials for the practical applications.     

高分子物理之流变学教学探讨

本文根据高分子行业的发展对人才的需求及高分子专业的培养目标定位,提出了在高等院校高分子专业本科阶段加强教授聚合物流变学内容的必要性,在介绍聚合物流变学的研究内容和研究方法的基础上归纳了其特点和重要性,根据高分子专业课程体系的承接性提出了流变学教学设置,进而结合高分子专业学生特点探讨了聚合物流变学本科教学的讲授内容和课时安排,并对教学过程中采用的教学方法和手段进行了探讨,还提出了在高分子实验中开设与流变学相关的实验促进教学的方法。     

Mg-Al MMH对除虫脲水悬浮剂流变性的影响

研究了Mg-Al型混合金属氢氧化物(MMH)质量分数(w)、温度和无机电解质对除虫脲水悬浮剂流变性的影响, 并采用Herschel-Buckley模型对流变曲线进行拟合. 实验结果表明, 稠度指数(KH)及屈服值(τH)均随w的增大而增大, w越大, 体系假塑性越明显, 且当w达到一定值后体系产生正触变性; 温度升高, KH和τH增大, 但不影响体系“剪切变稀”的假塑性特征和正触变性; 不同浓度的电解质对体系KH和τH的影响程度不同, 对于相同浓度的NaCl 和CaCl2, CaCl2对体系的影响更为显著, 但电解质的加入不改变体系“剪切变稀”的假塑性特征及正触变性.     

Effects of solid-liquid interface on the interfacial tension measured by micropipet technique

Measurement of interfacial tension (IFT) using the micropipet technique involves the solid-liquid interface. At equilibrium, oil-water interfacial tension is determined from the interface curvature and the critical pressure, according to the Young-Laplace equation. This paper aims to examine the possible contribution of the solid-liquid interface on IFT measurement. Three different experimental configurations are used to examine the sought effect. The three configurations are straight, concentric, and tapered pipets with diameters ranging from 2.5 to 30 microm. For all three configurations, the critical pressure is found to depend only on the pipet diameter. However, when the Young-Laplace equation is applied to determine the IFT, a significant error was noticed at small pipet diameters. The IFT error was described by an exponential function whose asymptote approached the independently determined IFT value with a sufficiently large pipet diameter. The IFT error is anticipated to arise from the layerlike effect of an "ultrastructured" liquid near the solid surface. The solid-induced error in oil-water IFT is noted to fade away at lowered IFT by the addition of surfactant.     

Ions at the water-oil interface: interfacial tension of electrolyte solutions

A theory, based on a modified Poisson-Boltzmann equation, is presented that allows us to calculate the excess interfacial tension of an electrolyte-oil interface accurately. The chaotropic (structure-breaking) ions are found to adsorb to the water-oil interface as the result of large polarizability, weak hydration, and hydrophobic and dispersion interactions. However, kosmotropic (structure-making) anions as well as potassium and sodium ions are found to be repelled from the interface. The adsorption of I(-) and ClO(4)(-) is found to be so strong as to lower the interfacial tension of the water-oil interface, in agreement with the experimental data. The agreement between the calculated interfacial tensions and the available experimental data is very good. The theory is used to predict the interfacial tensions of six other potassium salts, for which no experimental data is available at the moment.     

Investigations of the Rheology and Reactivity of Extrudable Wood-Resin Compounds

Summary. The extrusion of wood composites based on thermosetting resins is a new application in the field of wood plastic composites. To enable the extrusion of wood thermosetting compounds, it is necessary to know their reactivity and rheology well beforehand, to prevent the system curing inside the extruder. This study shows the different techniques that were adapted to allow in combination an estimation of the processing behaviour of wood-resin compounds in extrusion.