The effects of some factors on the rheological properties of the lyotropic liquid crystals formed in Brij97/NaDC/IPM/water system: compositions,temperature and polyphenols

In this paper, interaction between Brij97 and NaDC in mixed micelles was studied by surface tension method. Phase behavior for Brij97/NaDC/IPM/H₂O system was investigated at the desire molar ratio of α_NaDC?=?0.42 and the human body temperature of 37?°C. Hexagonal and cubic liquid crystal were found in this system analyzed by small angle x-ray scattering (SAXS). some factors were changed to affect the rheological properties of liquid crystal. Rheological investigations showed: The higher content of water and lower experimental temperature favored the greater values of shear viscosity and viscoelastic modulus; The sample was closer to the plastic fluid and was more likely to recover from disturbed state to equilibrium state at lower ratio of NaDC; The curcumin and TP can influence the shear viscosity, viscoelastic properties and phase transition temperature, even change the structure of liquid crystal. This supplies a way to adjust rheological properties, structure and even phase transition by altering those factors.     

Formation and properties of reverse micellar cubic liquid crystals and derived emulsions

The structure of the reverse micellar cubic (I2) liquid crystal and the adjacent micellar phase in amphiphilic block copolymer/water/oil systems has been studied by small-angle X-ray scattering (SAXS), rheometry, and differential scanning calorimetry (DSC). Upon addition of water to the copolymer/oil mixture, spherical micelles are formed and grow in size until a disorder-order transition takes place, which is related to a sudden increase in the viscosity and shear modulus. The transition is driven by the packing of the spherical micelles into a Fd3m cubic lattice. The single-phase I2 liquid crystals show gel-like behavior and elastic moduli higher than 104 Pa, as determined by oscillatory measurements. Further addition of water induces phase separation, and it is found that reverse water-in-oil emulsions with high internal phase ratio and stabilized by I2 liquid crystals can be prepared in the two-phase region. Contrary to liquid-liquid emulsions, both the elastic modulus and the viscosity decrease with the fraction of dispersed water, due to a decrease in the crystalline fraction in the sample, although the reverse emulsions remain gel-like even at high volume fractions of the dispersed phase. A temperature induced order-disorder transition can be detected by calorimetry and rheometry. Upon heating the I2 liquid crystals, two thermal events associated with small enthalpy values were detected: one endothermic, related to the "melting" of the liquid crystal, and the other exothermic, attributed to phase separation. The melting of the liquid crystal is associated with a sudden drop in viscosity and shear moduli. Results are relevant for understanding the formation of cubic-phase-based reverse emulsions and for their application as templates for the synthesis of structured materials.     

Rheological and thermal properties of a commercial liquid-crystalline polyesteramide

A commercial main-chain liquid-crystalline, naphthalene-based polyesteramide, was studied by three experimental techniques: extrusion capillary rheometry, dynamic viscoelasticity, and differential scanning calorimetry (DSC). From capillary rheometry a maximum at 360°C was observed in viscosity temperature curve. This result is compared with literature data for other thermotropics, and the possibility of a transition from a nematic to an isotropic phase is considered. The results obtained from dynamic viscoelasticity and DSC agree, and reveal the existence of a glass transition at 128°C (by DSC) and 137–147°C (by viscoelastic measurements, depending on frequency) as well as melting at 282°C. Annealing below 230°C produces two types of crystals, whereas annealing above this temperature gives rise to only one type of crystal, the melting temperature of which can be, depending on annealing time, as high as 340°C. The results are compiled in a phase diagram with six regions, four of them corresponding to the solid state, one to a liquid mesophase, and one to an isotropic phase.     

胶质液体泡沫的流变性

应用RV-30旋转粘度计和锥板式RS300应力控制流变仪, 采用稳态剪切方法和小振幅振荡剪切对胶质液体泡沫(CLA)体系的流变特性进行了系统分析, 讨论了温度、 相体积比(油相与水相体积比, PVR)和剪切速率对体系流变性质的影响. 稳态剪切实验结果表明, CLA体系表现出非牛顿流体特征, 其流变行为符合Herschel-Bulkley流变模式. 同时, CLA体系表现出剪切稀释特性, 不具有触变性. 粘弹性实验结果表明, 在低PVR(PVR=2~4)条件下, CLA无线性粘弹性区; 当PVR=8时, 表现出一定程度的粘弹性; 温度对体系的流变行为和粘弹性的影响不显著. 通过与高内相乳状液(HIPRE)体系比较, 发现CLA与HIPRE具有相似的流变特性, 这也说明两者在微观结构上具有一定的相似性.     

水解聚丙烯酰胺溶液粘弹特性的研究

通过锥板测量系统对水解聚丙烯酰胺(HPAM)溶液的粘弹性进行了研究.结果表明, 这种锥板测量系统能较灵敏地检测出溶液粘弹性结构的存在,并得到了聚合物溶液的弹性成份和粘性成份的关系.发现随着HPAM溶液浓度的增大,聚合物溶液的弹性成份起初迅速增大,随后增大的趋势变慢而趋于平缓,在经历一最大值后又略有下降.在剪切速率ṝ =0.36 s－1下,超高分子量的HPAM(M=1.65×107)溶液(c = 1.5 g·L－1)具有明显的粘弹特性;随着盐的加入,溶液的粘弹性下降,当盐浓度达到一定值的时候,溶液内部的网络结构遭到破坏,其弹性行为完全消失.对于聚丙烯酰胺(PAAM, M=2.0×105)溶液(c = 2.0 g·L－1)在剪切速率(ṝ=0.36～1.36 s－1)范围内没有观察到粘弹行为,只在ṝ≥1.65 s－1时,才能观察到微弱的粘弹现象.     

Shear-Induced "Melting" of an Aqueous Foam

We present diffusing-wave spectroscopy measurements of bubble dynamics in a continuously sheared aqueous foam. At slow strain rates, isolated clusters of bubbles intermittently rearrange from one solidly packed configuration to another, even though the macroscopic flow appears continuous. At fast rates, bubbles instead move smoothly and continuously throughout the entire foam. In other words, shear flow that appears macroscopically laminar is similarly laminar down to the bubble scale; effectively the foam "melts." The crossover to this regime can be understood in terms of elastic energy accumulation and viscous dissipation mechanisms. In particular, the strain rate needed for shear-induced melting to occur is set by the ratio of a yield strain to the rearrangement event duration. To explore the implications for macroscopic flow, we compare these bubble-scale dynamics directly with viscosity measurements. Copyright 1999 Academic Press.     

Rheological properties of lyotropic liquid crystals encapsulating curcumin

This study constructed new curcumin-loaded lyotropic liquid crystals containing pharmaceutically accepted oil, and ethyl oleate (EtOL). Three liquid crystalline phases including lamellar, hexagonal, and cubic phases were identified by means of the polarized optical microscopy and rheology method. By analyzing the shear viscosity (η_0.1), the viscosity of curcumin-liquid crystals is smaller than those without curcumin. Dynamic rheological results show that: Dissolved curcumin in EtOL can make the elastic modulus of hexagonal and cubic phase increase compared with that without curcumin, while the elastic modulus of lamellar phase decreases. Dissolved curcumin in Brij 97 can lead to the decreasing of the elastic modulus for cubic and lamellar phases, whereas it has little influence on hexagonal phase. When the curcumin is solubilized in both EtOL and Brij 97, the elastic modus of hexagonal phase increase, the elastic modus of lamellar and cubic phases decrease compared with that without curcumin. Furthermore, three temperature turning points were identified by the change in the slope of tanδ (G″/G′) for curcumin-hexagonal liquid crystal. These studies might be a help to study the storage of drug carrier and in vitro release properties of lyotropic liquid crystals containing curcumin.     

甘油单油酸脂/水立方液晶体系流变性质的研究

Monoglyceride (MO) can form various liquid crystalline phases spontaneously in the presence of various amount of water at room temperature. The appropriate compositions from binary phase diagram of MO/H2O were selected to form cubic phases. The selected systems were studied at different salt concentrations and pH value using rheological methods. There was a weak effect of salt on viscoelastic properties of cubic phases formed from MO/H2O system. Hexagonal phase was formed when pH value was decreased or increased. The viscoelasticity of cubic phases was different from that of hexagonal liquid crystals. Rheological properties of MO/H2O cubic phases were stable at pH and salt concentration similar to physiological condition.     

Cubic-Phase-Based Concentrated Emulsions

The effect of different types of added oil on the formation of a discontinuous micellar-type cubic phase was investigated in water-polyoxyethylene dodecyl ether (C(12)EO(25)) systems by phase study and small-angle X-ray scattering. The thermal stability of the cubic phase increases upon addition of oil, especially short-chain hydrocarbons. However, in the heptane system, the maximum melting temperature of the cubic phase is lower than that for decane due to the formation of a different liquid crystal phase. The effect of polyols on C(12)EO(25) cubic phases was also investigated. It was found that the thermal stability of the cubic phase decreases with polyol concentration. The destabilizing effect becomes large as the polyol molecule penetrates further into the surfactant palisade layer. Although the solubilization of oil in the cubic phase is very low, a large amount of excess oil can be incorporated and a transparent cubic-phase-based concentrated emulsion is formed. The transparency is attributed to the very small difference in the refractive indices between the cubic and excess-oil phases. Copyright 2000 Academic Press.     

Phase and rheological behavior of the polymerizable surfactant CTAVB and water

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.     

小形变时杨氏模量等于三倍的剪切模量

尽管高聚物是黏弹性材料,具有时间依赖性和温度依赖性,但在小形变时,弹性理论中的一些假定和定理仍能用来讨论黏弹性高聚物的形变。应力与应变之比是模量,在小形变时,单向拉伸的杨氏模量约等于三倍的剪切模量,E≈3G。     

Study on Non-Newtonian Behaviors of Lennard-Jones Fluids via Molecular Dynamics Simulations

Using nonequilibrium molecular dynamics simulations, we study the non-Newtonian rheological behaviors of a monoatomic fluid governed by the Lennard-Jones potential. Both steady Couette and oscillatory shear flows are investigated. Shear thinning and normal stress effects are observed in the steady Couette flow simulations. The radial distribution function is calculated at different shear rates to exhibit the change of the microscopic structure of molecules due to shear. We observe that for a larger shear rate the repulsion between molecules is more powerful while the attraction is weaker, and the above phenomena can also be confirmed by the analyses of the potential energy. By applying an oscillatory shear to the system, several findings are worth mentioning here:First, the phase difference between the shear stress and shear rate increases with the frequency. Second, the real part of complex viscosity first increases and then decreases while the imaginary part tends to increase monotonically, which results in the increase of the proportion of the imaginary part to the real part with the increasing frequency. Third, the ratio of the elastic modulus to the viscous modulus also increases with the frequency. These phenomena all indicate the appearance of viscoelasticity and the domination of elasticity over viscosity at high oscillation frequency for Lennard-Jones fluids.     

Pseudomonas aeruginosa attachment on QCM-D sensors: the role of cell and surface hydrophobicities

While biofilms are ubiquitous in nature, the mechanism by which they form is still poorly understood. This study investigated the process by which bacteria deposit and, shortly after, attach irreversibly to surfaces by reorienting to create a stronger interaction, which leads to biofilm formation. A model for attachment of Pseudomonas aeruginosa was developed using a quartz crystal microbalance with dissipation monitoring (QCM-D) technology, along with a fluorescent microscope and camera to monitor kinetics of adherence of the cells over time. In this model, the interaction differs depending on the force that dominates between the viscous, inertial, and elastic loads. P. aeruginosa, grown to the midexponential growth phase (hydrophilic) and stationary phase (hydrophobic) and two different surfaces, silica (SiO(2)) and polyvinylidene fluoride (PVDF), which are hydrophilic and hydrophobic, respectively, were used to test the model. The bacteria deposited on both of the sensor surfaces, though on the silica surface the cells reached a steady state where there was no net increase in deposition of bacteria, while the quantity of cells depositing on the PVDF surface continued to increase until the end of the experiments. The change in frequency and dissipation per cell were both positive for each overtone (n), except when the cells and surface are both hydrophilic. In the model three factors, specifically, viscous, inertial, and elastic loads, contribute to the change in frequency and dissipation at each overtone when a cell deposits on a sensor. On the basis of the model, hydrophobic cells were shown to form an elastic connection to either surface, with an increase of elasticity at higher overtones. At lower overtones, hydrophilic cells depositing on the hydrophobic surface were shown to also be elastic, but as the overtone increases the connection between the cells and sensor becomes more viscoelastic. In the case of hydrophilic cells interacting with the hydrophilic surface, the connection is viscous at each overtone measured. It could be inferred that the transformation of the viscoelasticity of the cell-surface connection is due to changes in the orientation of the cells to the surface, which allow the bacteria to attach irreversibly and begin biofilm formation.     

Nanoindentation creep of nonlinear viscoelastic polypropylene

Uniaxial tensile creep tests at various applied stresses were carried out to demonstrate that PP is nonlinear viscoelastic. A novel phenomenological model consisting of springs, dashpots, stress-locks and sliders was proposed to describe the nonlinear viscoelasticity. Indentation creep tests at different applied load levels were also performed on nonlinear viscoelastic PP. It was found that the shear creep compliance varies with the applied load level when the applied load is less than 5 mN, which means the indentation creep behavior was nonlinear. To find the real reason for the nonlinearity in indentation creep tests, the elastic modulus at various indentation depths was measured using continuous stiffness measurements (CSM). By analyzing the variation of elastic modulus with indentation depth, the nonlinearity of indentation creep behavior was proved to be caused by the non-uniform properties in the surface of the specimen rather than nonlinear viscoelasticity.     

Shear-induced topology changes in liquid crystals of the soybean lecithin/DDAB/water system

The viscoelastic behavior of the two different liquid crystalline lamellar phases and the liquid crystalline cubic phase of the mixed soybean lecithin/DDAB system in water was studied through rheology, with mechanical parameters studied as a function of composition. The swollen or diluted lamellar region is formed by vesicles, and its characteristic flow curve presents two-power law regions separated by a region where viscosity passes through a maximum. Yield stress and shear-dependent flow behavior were also observed. The microstructure suffers transformation under shear stress, and rheological response shifts from thixotropic to antithixotropic loops. Similar rheological behavior has been observed for samples in the collapsed or concentrated lamellar region, at the water-rich corner of the phase diagram. Vesicle formation may therefore occur by shearing the initial stacked and open bilayers. However, concentrated lamellar samples in the water-poor part of the phase diagram are less sensitive to shear effects and show plastic behavior and thixotropy. All lamellar samples manifest high elasticity. The dynamic responses of both lamellar topologies, i.e., vesicles and open bilayers, are comparable and exhibit an infinite relation time. The bicontinuous cubic, liquid crystalline phase is highly viscous. Its dynamic response cannot be modeled by a Maxwell model.     

混合表面活性剂双水相性质的研究

本文利用电导法及冷冻蚀刻实验技术研究了正负离子表面活性双水相上相中的液晶结构状态及其相关性质。在双水相相体积比一组成关系曲线上及上相电导率—组成曲线上,均存在明显的转折。转折处组成是有偏光现象的双水相与无偏光现象的双水相的分水岭,立方液晶导电能力与容纳水的能力强于层状液晶或六方液晶。冷冻蚀刻实验证实了无偏光现象的立方液晶的存在。本文对一些机理进行了讨论。     

Nuclear spin relaxation in poly(diethylsiloxane)

Earlier work showed that heating causes poly(diethylsiloxane) to undergo a first-order transition from a semicrystalline solid to a more mobile viscous—crystalline material. The latter is composed of two phases and analogies between polymer and liquid crystal morphology and behavior have been made. The viscous—crystalline phase in PDES appears to be unique since the literature is devoid of other documented examples. In this study, spin—lattice and spin—spin relaxation times were measured over a wide temperature range. They show a glass transition at 138°K, a crystal—crystal transition at 206°K, and a transition around 250°K which results from translational motion of the polymer chains with respect to each other. This motion is observed in the amorphous phase at a lower temperature than in the crystalline phase. Translational motion in the crystalline phase is observed on melting of the crystallites. The spin—spin data permitted monitoring of the molecular motions in each phase and the data suggest that these phases exert some influence on the molecular motions of each other. The viscous—crystalline phase in PDES may represent a unique model for studying and understanding “precrystalline” behavior and structure in amorphous solids.     

Operation of the quartz crystal microbalance in liquids: derivation of the elastic compliance of a film from the ratio of bandwidth shift and frequency shift

For a thin viscoelastic film deposited on a quartz crystal microbalance in a liquid environment, the change in dissipation induced by the presence of a film is proportional to the film's elastic compliance, Jf'. This surprising result is a consequence of the fact that the film is "clamped" by a viscous fluid.     

Aggregation of a peptide antibiotic alamethicin at the air-water interface and its influence on the viscoelasticity of phospholipid monolayers

The aggregation properties of an antibiotic membrane-active peptide alamethicin at the air-water interface have been studied using interfacial rheology and fluorescence microscopy techniques. Fluorescence microscopy of alamethicin monolayers revealed a coexistence of liquid expanded (LE) and solid phases at the surface concentrations studied. Interfacial oscillatory shear measurements on alamethicin monolayers indicate that its viscoelastic properties are determined by the area fraction of the solid domains. The role of zwitterionic phospholipids dioleoylphosphatidyl choline (DOPC) and dioleoylphosphatidyl ethanolamine (DOPE) on the peptide aggregation behavior was also investigated. Fluorescence microscopy of alamethicin/phospholipid monolayers revealed an intermediate phase (I) in addition to the solid and LE phase. In mixed monolayers of phospholipid (L)/alamethicin (P), with increase in L/P, the monolayer transforms from a viscoelastic to a viscous fluid with the increase in area fraction of the intermediate phase. Further, a homogeneous mixing of alamethicin/lipid molecules is observed at L/P > 4. Our studies also confirm that the viscoelasticity of alamethicin/phospholipid monolayers is closely related to the alamethicin/phospholipid interactions at the air-water interface.     

Viscoelastic and structural properties of a phenyl-modified polysiloxane system with a three-dimensional structure

The relationships between the viscoelastic and structural properties of glass-forming materials with polysiloxane bonds, which serve as network formers, and phenyl groups, which act as network terminators, are examined based on shear viscoelasticity, (29)Si MAS NMR, and GPC measurements during the early stages of the network-forming process. The viscosities of the present samples do not depend on the frequency at temperatures up to 200 degrees C, suggesting that the origin of the viscous flow does not include intermolecular entanglement. According to the results of the strain dependence of the elastic modulus, the bridging-oxygen number, and molecular weight, the present polysiloxane system has a complex structure, or distribution of various-sized molecules composed of a polysiloxane network with various dimensionalities, and furthermore an elementary process of the viscosity is simple flow of these molecules. The structural factors that determine the viscosity and its temperature dependence are categorized into the molecular size and the intramolecular structure by using a theory based on the free-volume model. The relationship between the viscosity and the structure around the glass transition temperature is quantitatively examined and it is concluded that introducing larger numbers of Ph groups makes the viscosity less sensitive to structural factors.