Wavy texture in pressure-driven startup flows of liquid crystalline polymer solutions through a slit cell: effects of polymer concentration and solution temperature

Dependences of wavy texture on polymer concentration and solution temperature were examined using aqueous solutions of hydroxypropylcellulose (HPC). The phase of aqueous solution of HPC varied from an isotropic (I) system to a liquid crystalline (LC) one through a biphasic (I+LC, LC+I) system with increasing the HPC concentration and/or decreasing the solution temperature. The wavy texture emerged not only in the LC system but also in the LC+I system. Furthermore, induction time of wavy texture was evaluated in terms of apparent shear strain. It is suggested that polydomain structures included in liquid crystalline systems and droplets of isotropic phase in biphasic systems affect the initial stage of emergence of wavy texture at low shear rates.     

Effect of fillers on the steady state rheological behaviour of liquid crystalline polymers

The effect of fillers on the flow curves of polymeric liquid crystals is investigated. Suspensions of polystyrene particles in liquid crystalline solutions of hydroxypropylcellulose (HPC) in water are used. By reducing the HPC concentration an isotropic solution can be prepared. It serves as a reference to isolate the effect of the isotropic/anisotropic structure of the suspending medium on the rheological behaviour. Suspensions in the isotropic solution behave as expected for filled viscoelastic matrices in general. In the anisotropic medium the shear rate rather than the shear stress seems to govern the changes in the relative viscosity. This behaviour is clearly different from isotropic viscoelastic media. The most dramatic effect however is that even small amounts of particles eliminate or drastically shift the region of negative normal stress differences. As far as the structure is concerned, microscopic observations show that particles align in anisotropic as well as in isotropic media. At rest or at relatively low shear stresses the liquid crystalline structure is, in the present case, hardly affected by the presence of the particles. If anything, it becomes more homogeneous. Received: 28 April 1998 Accepted: 28 July 1998     

A comparative study of the thermotropic mesomorphic tendencies and rheological characteristics of three cellulose derivates: Ethylene and propylene oxide ethers and an acetate butyrate ester

Samples of cellulose acetate butyrate (CAB) hydroxypropyl cellulose (HPC) and ethyl cellulose (EC) are contrasted with commercial (atactic) polystyrene (PS) and isotactic polypropylene (PP) in studies of (i) differential scanning calorimetry, (ii) quiescent polarized light microscopy (iii) optical retardation variation following an imposed stress field. It is concluced that HPC and EC are thermotropic liquid crystals, while CAB behaves in a manner similar to a vitrifying isotropic melt such as PS. Studies of the shear viscosity and dynamic viscosity indicate HPC and EC exhibit yield values while CAB shows a zero shear viscosity and Vinogradov-Malkin reduced viscosity curve identical to PS. The normal stress and extrudate swell behavior of CAB are also similar to PS. The HPC and EC exhibit substantially reduced extrudate swell. Measurement of the principal normal stress difference behavior of the HPC melt is troubled by the existence of yield values.     

Linear and nonlinear rheology of micellar solutions in the isotropic,cubic and hexagonal phase probed by rheo-small-angle light scattering

Aqueous solutions of a branched nonionic surfactant were studied in the isotropic, cubic and hexagonal phase by means of rheological and small-angle light scattering (SALS) experiments. The isotropic phase behaved like a Newtonian liquid. An increase of activation energy of viscous flow was found near the overlap concentration of spherical micelles, but no shear thinning was observed. The viscosity of low concentrated samples increased slightly when the lower critical solution temperature was approached. This increase of viscosity was much smaller compared to common nonionic surfactants. The cubic phases behaved as elastic solids with a high plateau modulus, and shear melting occurred at high shear stresses. The hexagonal phase showed complex behavior. Shear orientation could be achieved by large amplitude oscillatory shear and was proved by rheo-small-angle light scattering. Two orientations were observed, at first perpendicular to the flow direction, i.e., log-rolling state and, secondly, an in-shear-plane orientation parallel to the flow direction. The linear viscoelastic region of the hexagonal phase was extremely small and was detected by simultaneous rheo-small angle light scattering. Shear alignment lead to a decrease of the moduli.     

Rheological predictions of a transversely isotropic fluid model with extensible microstructure

A continuum extensible director theory was formulated to describe the isothermal, incompressible flow of uniaxial rodlike semiflexible liquid crystalline polymers. The model is strictly restricted to material that flow-align in shear, and that, in the absence of flow, are sufficiently far from the nematic-isotropic phase transition. The microstructure of the continuum is described by a variable length director, but the extensibility is finite. The model is an extension of the TIF (Transversely Isotropic Fluid) model of Ericksen (1960). The thermodynamic restrictions on the model parameters are found using the non-negative definiteness of the entropy production. The rheological material functions predicted by the model are calculated for steady simple shear and steady uniaxial extensional flows. In the rigid rod limit the model predictions agree with those of the TIF model, and for the finite extensibility case the model predictions are in agreement with those associated with flexible isotropic polymers: strong non-Newtonian shear viscosity, positive first normal stress differences, recoverable shear of order one, negative second normal stress differences, and a maximum in the steady uniaxial extensional viscosity.     

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通过实验方法研究了加入TiO2纳米颗粒的相变悬浮液流变特性. 研究表明,加入纳米颗 粒的相变悬浮液仍可被视为牛顿流体,温度对悬浮液的黏性系数有显著影响,其黏性系数随 温度变化的趋势与基液一致. 悬浮液的黏性随纳米颗粒浓度增加以非线性方式增加,当纳米 颗粒的质量浓度为5{\%}时,黏性的增量大约为23%.     

Orthogonal and parallel superposition measurements on lyotropic liquid crystalline polymers

 Mechanical spectroscopy is used to probe the structure of lyotropic liquid crystalline polymers during flow and after the cessation of flow. The oscillatory flow is either parallel or perpendicular to the steady-state flow. The resulting moduli provide information about the time- and shear-dependent microstructure, including anisotropy. Two different concentrations of poly(benzylglutamate) (PBG) in m-cresol and a concentrated hydroxypropylcellulose (HPC) solution, also in m-cresol, are investigated. In all cases, the orthogonal superposition moduli evolve differently from the parallel ones. The former are less sensitive to the flow-induced changes in structure than the latter ones. Together with the lack of sensitivity of the superposition moduli to texture refinement during flow, this suggests a strong relation between director orientation and superposition moduli. After the cessation of flow the parallel moduli decrease for the PBG solutions, whereas the opposite is observed in the HPC solutions. A comparison with the orthogonal moduli provides a direct measure of anisotropy. At rest, the PBG solutions tend toward a higher degree of anisotropy while the HPC solutions become more isotropic. In the latter systems, all moduli are much larger, reflecting a larger contribution from the texture. Received: 8 July 1999/Accepted: 1 October 1999     

Quantitative NMR velocity imaging of a main-chain liquid crystalline polymer flowing through an abrupt contraction

 The flow of isotropic and liquid crystalline (LC) hydroxypropylcellulose (HPC) aqueous solutions into an abrupt axisymmetric contraction has been quantitatively measured by pulsed-field-gradient NMR techniques. Steady-state axial velocity profiles, acquired upstream of the contraction, reveal a large contraction entry length for the LC solution. This entry flow field exists over an order of magnitude change in flow rate and is attributed to elasticity that is associated with polydomain liquid crystallinity. Pronounced, off-centerline velocity maxima (in an axisymmetric flow field) were present upstream of the contraction, in the entry flow region. Apparently, a more viscous and elastic core of fluid was present along the centerline; this fluid resisted elongational strain more than the fluid closer to the walls. Quantitative velocity profiles were extracted from displacement distributions and corrected for elongational dispersion. The isotropic solution velocity profiles matched those obtained from viscoelastic simulations using an approximate Doi-Edwards model, parameterized with independent rheological data. Received: 29 April 1999/Accepted: 30 August 1999     

向列相溶致液晶旋转黏度研究

溶致液晶具有良好的生物相容性、无毒性、生物降解性以及光学、电磁学各向异性等, 在细胞相互作用、神经刺激传递、脂肪吸收、药物智能输运等生命活动研究、医药工程和液晶显示等领域有广泛应用. 本文采用旋转磁场法测得溶致液晶日落黄在不同温度和溶液浓度下向列相时旋转黏度, 并结合溶致液晶分子自组装过程, 理论分析了溶致液晶向列相旋转黏度随温度和溶液浓度的变化规律. 研究结果表明: 溶致液晶旋转黏度与液晶分子自组装柱状体平均长度的平方呈正比增大关系, 随溶液浓度的增大而增大, 随温度的升高表现出指数减小的规律. 构建了与向列相溶致液晶温度和浓度相关的旋转黏度经验表达式, 经验表达式计算结果与实验值吻合较好, 最大误差仅为18.56${\%}$. 提出采用旋转流变仪间接获得溶致液晶剪切能的新方法, 溶致液晶剪切能随溶液浓度的增大而增大, 但在实验温度范围内, 溶致液晶剪切能几乎不随温度而改变. 利用旋转流变仪间接获得的溶致液晶剪切能与报道的利用X-Ray检测所得的结果之间最大误差仅为3${\%}$. 成功地利用了液晶分子自组装能力随温度的变化规律来研究柱状体长径比对旋转黏度的影响规律, 创新地提出了"一步法"测量研究, 大大减少相关实验研究的成本和复杂性.      

Determination of thermal conductivities of Sn–Zn lead-free solder alloys with radial heat flow and Bridgman-type apparatus

The variations of thermal conductivities of solid phases versus temperature for pure Sn, pure Zn and Sn–9 wt.% Zn, Sn–14 wt.% Zn, Sn–50 wt.% Zn, Sn–80 wt.% Zn binary alloys were measured with a radial heat flow apparatus. The thermal conductivity ratios of liquid phase to solid phase for the pure Sn, pure Zn and eutectic Sn–9 wt.% Zn alloy at their melting temperature are found with a Bridgman-type directional solidification apparatus. Thus, the thermal conductivities of liquid phases for pure Sn, pure Zn and eutectic Sn–9 wt.% Zn binary alloy at their melting temperature were evaluated by using the values of solid phase thermal conductivities and the thermal conductivity ratios of liquid phase to solid phase.     

Experimental study of stability in a layer of a model alloy with a liquid miscibility gap

The stability of Rayleigh-Bénard convection in a transparent model alloy was investigated with holographic interferometry. The dispersed minority phase is the heavier component. The majority component is lighter. A vertical temperature difference was applied to the liquid layer keeping the hot temperature always above phase separation. The upper cold side temperature was kept above or below the phase separation temperature. Fluid separation occurs when the cold temperature drops below consolute temperature. When the liquid is kept at higher than consolute temperature, it is noticed that the stability of the layer is increased when the average temperature approaches the consolute temperature. Received on 13 January 1997     

Polypropylene-polyethylene blends

Summary Die swell behaviour and morphology of melt blends of isotactic polypropylene (PP) and high density polyethylene for pure polymers and blends with 25, 50 and 75 weight % PP are described in the present study. A light interference contrast microscopy technique was used for the morphological characterization of melt blends and extrudate samples of the blends obtained with an Instron capillary rheometer. The results indicate that the domains from blends where the dispersed phase has higher viscosity than the continuous phase remain as continuous domains in the extrudate whereas domain destruction takes place when blends where the continuous phase has the higher viscosity are extruded.The die swell behaviour as well as the fiber forming properties of extrudates of melts having unstable domains extruded at high shear stresses resemble the behaviour of homopolymers, whereas samples with stable domains are significantly different, die swell increases with temperature at constant shear stress and stable fibers cannot be obtained after necking.With 10 figures and 1 table     

Transient rheological behaviour of poly-para-henylenetherephthalamide (PpPTA) in sulphuric acid

Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules.     

Investigation of viscosity and thermal conductivity of alumina nanofluids with addition of SDBS

The present study focused on thermal conductivity and viscosity of alumina nanoparticles, at low volume concentrations of 0.01–1.0 % dispersed in the mixture of ethylene glycol and water (mass ratio, 60:40). Sodium dodeobcylbenzene sulfonate (SDBS) was applied for better dispersion and stability of alumina nanoparticles and study of its influence on both thermal conductivity and viscosity. The thermal conductivity established polynomial enhancement pattern with increase of volume concentration up to 0.1 % while linear enhancement was obtained at higher concentrations. In addition, thermal conductivity was enhanced with the rise of temperature. However, the augmentation was negligible compared to that obtained with increase of volume concentration. In contrast, viscosity data showed remarkable reduction with increase of temperature. Meanwhile, viscosity of nanofluids enhanced with loading of alumina nanoparticles. Thermal conductivity and viscosity measurements showed higher values over theoretical predictions. Results showed SDBS at different concentrations has distinct influence on thermal conductivity and viscosity of nanofluid.     

Influence of degree of sulfation on the rheology of cellulose nanocrystal suspensions

The rheology and microstructure of two different cellulose nanocrystals (CNC) samples possessing different degrees of sulfation are studied over a broad concentration range of 1 to 15 wt%. CNC suspensions are isotropic at low concentration and experience two different transitions as concentration increases. First, they form chiral nematic liquid crystals above a first critical concentration where the samples exhibit a fingerprint texture and the viscosity profile shows a three-region behavior, typical of liquid crystals. By further increasing the concentration, CNC suspensions form gels above a second critical concentration, where the viscosity profile shows a single shear-thinning behavior over the whole range of shear rates investigated. It has been found that the degree of sulfation of CNC particles has a significant effect on the critical concentrations at which transitions from isotropic to liquid crystal and liquid crystal to gel occur. Rheological properties and microstructure of these suspensions have been studied using polarized optical microscopy combined with rheometry.     

Pressure-driven startup flows of liquid crystalline polymers through slit cells

A wavy texture occurs in the flows of liquid crystalline polymers through a slit cell. In the present paper the development of the wavy texture is examined in pressure-driven startup flows for four types of slit cells, using a liquid crystalline solution of 50 wt% hydroxypropylcellulose (HPC). There exists a comparatively long induction period until the wavy texture appears after the startup of the flow, and the induction time decreases with increasing apparent shear rate. However, it is found that the apparent shear strain at which the wavy texture emerges is independent of the apparent shear rate though the value of the apparent shear strain slightly varies with the type of flow cell. Furthermore, the light scattering experiments are carried out to examine the structure of wavy texture. After the startup of the flow, a homogeneous pattern of the light scattering quickly shrink in size and a spike pattern perpendicular to the flow direction is emphasized. While the wavy texture is seen, the ellipsoidal pattern of light scattering oscillates with the same frequency as the passage of the wavy texture. A structure of scattering objects in the wavy texture is proposed, based on the observation of change in the light scattering pattern with time.     

Thermoreversible gelation of hydroxypropylcellulose aqueous solutions

The thermoreversible gelation of hydroxypropylcellulose (HPC)/water solutions is investigated by means of rheological and optical techniques. The linear viscoelasticity of solutions at different concentrations is measured during heating ramps from room temperature. The experimental results suggest that the solution microstructure changes according to two sequential steps, i.e., precipitation and gelation. Temperature, temperature rate of change, and concentration are found to be relevant parameters controlling the phase transition.     

The relevance of entry flow measurements for the estimation of extensional viscosity of polymer melts

The extensional viscosity of some flexible chain polymers and a thermotropic liquid crystalline polymer was measured in uniaxial extensional flow at constant extension rate. Power law functions were found for the dependence of the extensional viscosity at constant accumulated strain on strain rate. The stress growth curves were compared with measurements in axisymmetric entry flow, where both elongation and shear occur. The comparison showed that the values of the extensional viscosity calculated from the measurements in the entry flow correspond to the ones calculated from the viscosity growth measured in uniaxial elongation and averaged over extensional strain equal to what is accumulated on the fluid as it flows from the barrel into the capillary.     

A Pore Scale Study of Non-Newtonian Effect on Foam Propagation in Porous Media

CO₂ injection is one of the most promising techniques to enhance oil recovery. However, an unfavorable mobility ratio, reservoir heterogeneity and gravity segregation can reduce the macroscopic sweep efficiency. In situ foaming of injected CO₂ is the method that has the most potential for improving sweep efficiency based on controlling CO₂ mobility. This study investigates the foaming behavior of N,N,N′-trimethyl-N′-tallow-1,3-diaminopropane (DTTM) surfactant with CO₂ in a transparent porous microflow model with natural rock pore structures. It focuses on the effect of the salinity induced non-Newtonian behavior of DTTM solution on foam propagation. The performance of foams stabilized by 0.5 wt% DTTM solution over the viscosity range from 0.71 (at 5 wt% NaCl) to 41 cp (at 20 wt% NaCl) was compared with conventional polymer-enhanced foams whose liquid phase contained a commonly used foaming surfactant, C15–18 Internal Olefin Sulfonate (C15–18 IOS) and a hydrolyzed polyacrylamide. Such comparisons have also provided insight into the respective impacts of liquid phase viscosification by worm-like surfactant micelles and polymer on foam texture associated with its rheological characteristics. It was found that at low aqueous phase viscosity (injection liquid viscosity of 0.71 cp) the maximum achievable viscosity of DDTM foam was around 1000 cp, which was 80 times IOS stabilized foam. The interfacial tension of DTTM was higher than that of IOS, resulting coarser foam texture and higher individual lamella resistance. An increase in DTTM solution viscosity by a factor of 33 decreased foam generation and viscosity for gas injection. This was not observed for the simultaneous injection of gas and DTTM solution. Overall, the effect of liquid phase viscosity on transient foam behavior during gas injection is similar for both DTTM and IOS regardless of the difference in the nature of viscosifying agents (WLM vs 3330 s polymer). An increase in gas injection pressure without liquid injection delayed foam propagation and reduced the magnitude of foam viscosity. The results from this study indicated that DTTM surfactant is an important alternative to commercially available polymers that have been used to enhance foam performance in porous media. This particular surfactant type also overcomes several disadvantages of polymers such as limited temperature and salinity tolerance, shear degradation, and filtering in low permeability formations.

     

On the time-dependency of the flow-induced dynamic moduli of a liquid crystalline hydroxypropylcellulose solution

Some unusual rheological features of a liquid crystalline solution of hydroxypropylcellulose (HPC) in water have been investigated. Measurements have been performed by using a variety of different apparatuses with cone and plate geometries. Particular attention has been devoted to the experimental procedures, including the use of different sealing techniques, which are necessary to avoid solvent evaporation during the very long transients. Shear fracture effects, and their dependence on the type of sealing agents have also been studied. In steady shear, the HPC solution shows some rheological features which are common to other lyotropic systems, such as a three-region viscosity curve, and a double sign change in the first normal stress difference vs shear rate curve. The structural changes which take place after cessation of shear flow have been investigated by following the evolution of the dynamic moduli as a function of the time elapsed after the shear flow is stopped. It was found that the rate of the previously applied shear strongly affects both the kinetics and the asymptotic, long time values of the dynamic properties. Possible explanations for such behavior in terms of microstructure evolution are presented and discussed.