新型成膜法的SAW气体传感器聚合物膜的粘弹性分析

An analysis of the response of surface acoustic wave sensors coated with polymer film based on new coating deposition (self-assemble and molecularly imprinted technology) is described and the response formulas are hence deduced. Using the real part of shear modulus, the polymer can be classified into three types: glassy film, glassy-rubbery film and rubbery film. Experimental results show that the attenuation response is in better consistence with the simulation than in Martin's theory, but the velocity response does not accord with the calculation exactly. Maybe it is influenced by the experimental methods and environment. In addition, simulations of gas sorption for polymer films are performed. As for glassy film, the SAW sensor response increases with increasing film thickness, and the relationship between the sensor response and the concentration of gas is pretty linear, while as for glassy-rubbery film and rubbery film, the relationship between the sensor sensitivity and concentration of gas is very complicated. The ultimately calculated results indicate that the relationship between the sensor response and frequency is not always linear due to the viscoelastic properties of the polymer.     

Phase behavior of polystyrene acrylonitril copolymer and polymethylmethacrylate blends under shear

Polymer blends undergo external stresses such as pressure and shear in course of processing cycles. The knowledge of their phase behavior at each step of these cycles is crucial for understanding their physical properties and eventually improves their performance in practical applications. The effects of shear on the phase diagram of binary polymer blends are considered. A theoretical formulism is used upon which the free energy is the sum of two terms. The first term is modeled with the Flory–Huggins free energy of mixing and describes the thermodynamic behavior of the system in the quiescent state. The second term represents the excess free energy stored during flow. In the presence of shear flow, the excess free energy is expressed in terms of the viscosity and the shear modulus. Both quantities depend on composition and shear rate. The curvature of the variation of viscosity versus composition has a tremendous impact upon the nature of phase separation. Phase diagrams are described by the spinodal curves and show for the case considered here miscibility enhancement with increasing shear rate. A good correlation is found with experimental data of the literature on blends of polystyrene acrylonitril copolymer and polymethylmethacrylate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Morphology and Properties of Particulate Filled Polymers

Although the structure of particulate filled polymers is usually thought to be very simple, often structure related phenomena determine their properties. Segregation occurs only when long flow paths and large particles are used in production. The occurrence and extent of aggregation depend on the relative magnitude of attractive and separating forces, which prevail during the homogenization of the composite; the balance of adhesive and shear forces determines structure. Fillers of small particle size always aggregate, usually leading to decreased strength and especially low impact resistance. Anisotropic particles (talc, mica, short fibers) are orientated during processing. ESR is a relatively simple technique for the estimation of orientation and orientation distribution, which are determined by processing conditions, i.e. flow pattern, shear conditions, mold filling rates, cooling conditions, etc. The orientation of the particles strongly affects composite stiffness and strength. In practice, often several factors simultaneously influence the properties of products prepared from particulate filled polymers. Separation of the effects of the influencing factors is difficult, although such knowledge would help to control composite properties. The structure and properties of injection and compression moulded PP composites containing CaCO₃ or talc differs considerably from each other. The aggregation of CaCO₃, the nucleating effect and the orientation of talc affect product properties. The latter are also influenced by the skin-core structure developing during injection molding as well as by the orientation of the polymer. An example is discussed in this paper, which facilitates the identification of the effect of these factors with the help of a simple model and indicates a way in which product properties can be controlled.     

Rheology of concentrated carbon nanotube suspensions

The rheological properties of non-Brownian carbon nanotube suspensions are measured over a range of nanotube volume fractions spanning the transition from semidilute to concentrated. The polymer-stabilized nanotubes are "sticky" and form a quiescent elastic network with a well-defined shear modulus and yield stress that both depend strongly on nanotube volume fraction with different but related critical exponents. We compare controlled-strain-rate and controlled-stress measurements of yielding in shear flow, and we study the effect of slow periodic stress reversal on yielding and the arrest of flow. Our measurements support a universal scaling of both the linear viscoelastic and steady-shear viscometric response. The former allows us to extract the elastic shear modulus of semidilute nanotube networks for values that are near or below the resolution limit of the rheometers used, while the latter provides a similar extrapolation of the yield stress. A simple scaling argument is used to model the dependence of yield stress and elastic modulus on concentration.     

The Effects of Extensional Flow and Hydrodynamic Interaction on the Nonequilibrium Brownian Dynamics of Dendrimers. A Bead‐Spring Model for Dendrimeric Molecules

We present the effects of incorporating hydrodynamic interactions into the nonequilibrium Brownian dynamics model describing the rheological properties of dendrimers under simple shear flow. The model response to uniaxial extensional flow is considered and compared with the extensional flow behavior of conventional linear molecules. The dendrimers are characterized by low viscosities and display little visco‐elasticity which makes them attractive materials from the stand‐point of energy‐intensive polymer forming processes.     

Stokesian Dynamics Simulations of Ferromagnetic Colloidal Dispersions Subjected to a Sinusoidal Shear Flow

We have conducted Stokesian dynamics simulations to investigate the dynamic properties of ferromagnetic colloidal dispersions subjected to a sinusoidal shear flow. Thick chain-like cluster formation is significantly influenced by an oscillatory shear flow even if the amplitude is relatively small, since the internal structures of thick chain-like clusters are highly sensitive to the change in the direction of the shear flow. The motion of thick chain-like clusters is out of phase to a sinusoidal shear rate, and the phase difference is strongly correlated with that of the viscosity and normal stress coefficients. The viscoelastic properties become more apparent with decreasing frequency of the oscillatory shear flow, since such properties have a strong relationship with the thick chain-like cluster formation. In other words, since thick chain-like clusters are more stable for the case of a smaller frequency shear flow, such stable clusters induce significant viscoelastic properties of ferromagnetic colloidal dispersions in a strong, applied magnetic field. Copyright 2000 Academic Press.     

Dynamics of chiral liquid crystals under applied shear

We simulate the alignment dynamics of cholesteric (chiral) rod-like liquid crystals by using a Landau-de Gennes (LdG) expression for microstructure evolution in response to flow. This study is motivated by recent advances in novel cholesteric nanorod dispersions. Prior work on the modelling of cholesterics has suffered from the restriction of helicity to only a single direction, often with a pre-imposed pitch, due to numerical difficulties. This has severely limited cholesteric modelling in regard to both accuracy and experimental relevance. Our simulations avoid this limitation. Relevant forces on rods include solvent-rod drag, nematic alignment, microstructure elasticity and chiral twist. Phase diagrams are developed to demonstrate the response of these systems to variations in chiral and flow forces. Our results indicate that for low shear rates, chiral and elastic forces prevent the rods from moving in response to flow. At high shear rates, the rods tumble and form unique transient structures (combinations of tumbling and cholesteric phases) as flow forces and chiral forces compete. Even if slight alignment is induced at the boundaries, the phase diagram substantially changes, chiefly by constraining the possible chiral phases. This work has immediate relevance to applications which exploit the optical properties of films solidified from cholesteric dispersions.     

Shear and dilatational relaxation mechanisms of globular and flexible proteins at the hexadecane/water interface

Proteins adsorbed at fluid/fluid interfaces influence many phenomena: food emulsion and foam stability (Murray et al. Langmuir 2002, 18, 9476 and Borbas et al. Colloids Surf., A 2003, 213, 93), two-phase enzyme catalysis (Cascao-Pereira et al. Biotechnol. Bioeng. 2003, 83, 498; 2002, 78, 595), human lung function (Lunkenheimer et al. Colloids Surf., A 1996, 114, 199; Wustneck et al.; and Banerjee et al. 2000, 15, 14), and cell membrane mechanical properties (Mohandas et al. 1994, 23, 787). Time scales important to these phenomena are broad, necessitating an understanding of the dynamics of biological macromolecules at interfaces. We utilize interfacial shear and dilatational deformations to study the rheology of a globular protein, lysozyme, and a disordered protein, beta-casein, at the hexadecane/water interface. Linear viscoelastic properties are measured using small amplitude oscillatory flow, stress relaxation after a sudden dilatational displacement, and shear creep response to probe the rheological response over broad experimental time scales. Our studies of lysozyme and beta-casein reveal that the interfacial dissipation mechanisms are strongly coupled to changes in the protein structure upon and after adsorption. For beta-casein, the interfacial response is fluidlike in shear deformation and is dominated by interfacial viscous dissipation, particularly at low frequencies. Conversely, the dilatational response of beta-casein is dominated by diffusion dissipation at low frequencies and viscous dissipation at higher frequencies (i.e., when the experimental time scale is faster than the characteristic time for diffusion). For lysozyme in shear deformation, the adsorbed protein layer is primarily elastic with only a weak frequency dependence. Similarly, the interfacial dilatational moduli change very little with frequency. In comparison to beta-casein, the frequency response of lysozyme does not change substantially after washing the protein from the bulk solution. Apparently, it is the irreversibly adsorbed fraction that dominates the dynamic rheological response for lysozyme. Using stress relaxation after a sudden dilatational displacement and shear creep response, the characteristic time of relaxation was found to be 1000 s in both modes of deformation. The very long relaxation time for lysozyme likely results from the formation of a glassy interfacial network. This network develops at high interfacial concentrations where the molecules are highly constrained because of conformation changes that prevent desorption.     

Properties of mixed protein/surfactant adsorption layers

The adsorption isotherms, adsorption kinetics and surface rheological properties of β-lactoglobulin, β-casein, in the absence and presence of Tween 20 were measured. To study the adsorption process (isotherms and kinetics) at the water–air interface the pendant drop technique (axial drop shape analysis, ADSA), and ring tensiometry were used. The surface shear rheological parameters were measured with a torsion pendulum set-up. Also, data of the equilibrium film thickness and surface diffusion coefficients obtained from fluorescence recovery after photobleaching (FRAP) measurements are used to understand the competitive adsorption mechanism. The adsorption process and shear rheological behaviour of the studied systems show a rather complex behaviour which depends most of all on the system's composition. At high protein or surfactant content the behaviour is controlled by the main component while for the more mixed systems the adsorption process is complex and consists of partial adsorption, surfactant–protein interaction and protein rearrangement as a function of surface coverage. The results obtained illustrate that all these processes must be taken into account in future new theoretical models to be derived for such systems.     

Fiber spinning from the nematic melt. V. Flow instabilities in the 75:25 copolyester of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid

We have investigated the rheological properties of the Celanese copolyester with the composition 75 mol% p-hydroxybenzoic acid and 25 mol% 2-hydroxy-6-naphthoic acid (designated as 75HBA/25HNA). Three different samples having inherent viscosities 3.0, 6.0, and 9.2 dL/g were studied. A flow instability is observed at low shear stress which produces an irregularity in the fiber diameter. The surface irregularity becomes less pronounced above a minimum shear stress, indicating that the flow instability originates in the capillary. For these nematic melts, the minimum shear stress marking the onset of more regular flow is found to decrease with increasing temperature and with decreasing inherent viscosity of the copolyester. The die swell ratio of extrudates decreases with increasing shear stress. Fibers were spun from the samples having η_inh = 9.2 and 3.0 dL/g. The initial modulus and tenacity to break for 75HBA/25HNA fibers spun at sufficiently high shear stress to produce smooth filaments are significantly lower than the values we previously reported for fibers of the 58HBA/42HNA copolyester. Moreover, the optimum properties are obtained at relatively low spin-draw ratios. The 75HBA/25HNA polyester also exhibits a yield stress which decreases with increasing temperature. This observation indicates the presence of crystallities at the test temperatures. We believe that the higher content of HBA in the present copolymer gives rise to crystallization of HBA blocks in the thread line and that defects are introduced at higher spin-draw ratios which cause the mechanical properties to become worse.     

Understanding of surface tension?

The importance of the molar dimensions for surface properties of not too large molecules is stressed. The understanding of surface properties of pure liquids is described in molar units with a simple model of normal liquids. The increasing knowledge makes it necessary to use idealized models. A hypothesis is given for the temperature constancy of the surface energy of small molecules without H-bonds, and a model is developed for the free energy σ_m and its temperature dependency. This seldom example of the direct measurement of the isothermic work or the free energy could help to illustrate the difference between energy and free energy. Received: 24 July 2000 Accepted: 26 October 2000     

Shear-induced deformations of polyamide microcapsules

The application of microcapsules for technical, cosmetic and pharmaceutical purposes has attracted increased interest in recent years. The design of new capsule types requires a profound knowledge of their mechanical properties. Rheological studies provide interesting information on intrinsic membrane properties and this information can be used to avoid premature release of encapsulated compounds due to the action of external mechanical forces (stirring, swallowing, spreading). In this publication we report a systematic study of polyamide microcapsules. These particles were synthesized by reacting 4-aminomethyl-1,8-diaminooctane and sebacoyl dichloride at the interface between silicone oil and water. Two different experiments were performed to get information on the mechanical properties of the capsule walls. First of all, we used an optical rheometer (rheoscope) to observe the capsule deformation and orientation in shear flow. The polymerization kinetics, relaxation properties, the regime of linear-viscoelastic behavior and the shear modulus of the flat membranes were independently measured in an interfacial rheometer. Both experiments gave complementary results. It turned out that the two-dimensional elongational modulus was about 3–4 times larger than the shear modulus. This result is in fairly good agreement with a theoretical model recently proposed by Barthès-Biesel. Due to the simple synthesis and well-defined structure, polyamide microcapsules can also serve as simple model systems to understand the complicated flow properties of red blood cells. Received: 5 July 1999/Accepted in revised form: 30 August 1999     

Separating viscoelastic and compressibility contributions in pressure-area isotherm measurements

Monolayers of surface active molecules or particles play an important role in biological systems as well as in consumer products. Their properties are controlled by thermodynamics as well as the mechanical properties of the interface itself. For insoluble species forming Langmuir monolayers, surface pressure-area isotherms are typically used to characterize the thermodynamic state. A Langmuir trough equipped with a Wilhelmy plate is often used for such measurements. However, when Langmuir interfaces are compressed and become more structured, the elastic response of these interfaces can interfere with the measurement of the surface pressure-area isotherm, even when the compression speed is slow. Recent reports of compression data for highly elastic interfaces revealed a dependence of the apparent surface pressures on the geometry of the measurement trough. In the present work, this dependence is investigated by considering adequate constitutive models. Since deformations in such compression experiments can be large, linearized versions of the Kelvin–Voigt model do not suffice. We develop a framework for quasi-linear constitutive models by choosing suitable non-linear strain tensors, adequately separating the shear and dilatational effects in a frame invariant manner. The proposed constitutive models can be used as building blocks to describe viscoelastic behavior as well. The geometry dependence in isotherm measurements is then shown to be a consequence of varying contributions of the isotropic surface pressure and extra shear and dilatational elastic stresses. Using these insights, an approach is proposed to obtain the intrinsic surface pressure-area isotherms for elastic interfaces. As a case study, experimental data on graphene oxidesheets at the air–water interface is investigated to evaluate the proposed model.     

Viscoplastic flow and shear thickening in concentrated diblock copolymer solutions

Concentrated (typically 6%) solutions of a polystyrene-polyisoprene diblock copolymer in low viscosity paraffinic solvents form a micelle system by precipitating the polystyrene blocks, whereas the polyisoprene blocks are in solution. Besides viscoplastic behavior without thixotropy, this system exhibits a pronounced shear thickening in steady-state shear flow. The micelles are stable up to shear rates of more than 10⁵ s^–1. The properties of the solutions, especially the shear-thickening behavior, depend on the thermal history of the samples as well as on the solvent properties and are sensitive to flow field disturbances occurring in rotational viscometer devices with a profiled surface structure as commonly used to avoid wall slip in dispersed materials. The shear thickening is found to be related to the formation of a long-range ordered structure which also gives rise to the yield point. This long-range order enables aggregate flow with less energy dissipation at low shear rates. Shear-induced break-up of the aggregates appears as a shear-thickening transition which is observed in different types of flow fields.     

Permeative flows in cholesterics: shear and Poiseuille flows

By using a lattice Boltzmann scheme that solves the Beris-Edwards equations of motion describing liquid-crystal hydrodynamics, we study the response of cholesterics to shear and Poiseuille flows. The geometry we focus on is a flow along the direction of the helical axis, which is known to give rise to permeation. For both shear and Poiseuille flow we find that the boundary conditions on the director field are crucial in determining the rheological properties of the liquid crystal. For helices pinned at the boundaries, a small forcing leads to a large viscosity increase whereas a stronger forcing induces a sharp decrease towards the Newtonian value. This shear thinning behavior is in agreement with experiments and previous analytic results. If, on the other hand, the director is free to rotate at the walls, different behaviors are found depending on the symmetry of the steady-state primary flow. Some of the cases considered are compared to a similar imposed flow but with the helix lying perpendicular to the plates, for which no viscosity increase is observed.     

Rheology and thermal stability of polylactide/clay nanocomposites

Polylactide/clay nanocomposites (PLACNs) were prepared by melt intercalation. The intercalated structure of PLACNs was investigated using XRD and TEM. Both the linear and nonlinear rheological properties of PLACNs were measured by parallel plate rheometer. The results reveal that percolation threshold of the PLACNs is about 4 wt%, and the network structure is very sensitive to both the quiescent and the large amplitude oscillatory shear (LAOS) deformation. The stress overshoots in the reverse flow experiments were strongly dependent on the rest time and shear rate but shows a strain-scaling response to the startup of steady shear flow, indicating that the formation of the long-range structure in PLACNs may be the major driving force for the reorganization of the clay network. The thermal behavior of PLACNs was also characterized. However, the results show that with the addition of clay, the thermal stability of PLACNs decreases in contrast to that of pure PLA.     

Photoluminescence investigations of ZnO micro/nanostructures

Zinc oxide (ZnO) is probably one of the most researched wide bandgap semiconductors in the last decades due to its unique characteristics in terms of low production cost, high availability, bioinertness, and especially its interesting optical properties. Although this semiconductor is considered an ‘old’ material and is known to possess such unique properties for more than three decades, the interest was renewed because of the advances in nanotechnology and the possibility to be produced in a vast number of nanostructures with tunable properties. An adequate knowledge of the nanomaterials’ optical response is mandatory for assessing and optimizing their functionalities towards different applications. Although the photoluminescence properties of ZnO bulk materials have been known from several decades, quite a number of open questions remains, namely regarding the nature of defects responsible for the broad luminescence bands frequently observed in the visible spectral region. With the effects of reducing the dimensionality of the material to the nanoscale, changes may arise in the luminescence outcome due to the role of the surface/interface characteristics. Indeed, the surface phenomena can strongly affect the nanostructure properties and can be used to tailor them, consequently having a profound influence on the performance of the devices where the nanostructures are employed. Hence, in this article, an overview of the fundamental properties of ZnO, with emphasis on the main optical recombination mechanisms, both in bulk and at the nanoscale, is provided to disclose some of the current knowledge in this subject. In addition, some examples of the myriad of applications where this semiconductor has been exploited are also discussed.     

The effect of particle shape on the structure and rheological properties of carbon-based particle suspensions

The structure and rheological properties of carbon-based particle suspensions, i.e., carbon black(CB), multi-wall carbon nanotube(MWNT), graphene and hollow carbon sphere(HCS) suspended in polydimethylsiloxane(PDMS), are investigated. In order to study the effect of particle shape on the structure and rheological properties of suspensions, the content of surface oxygen-containing functional groups of carbon-based particles is controlled to be similar. Original spherical-like CB(fractal filler), rod-like MWNT and sheet-like graphene form large agglomerates in PDMS, while spherical HCS particles disperse relatively well in PDMS. The dispersion state of carbon-based particles affects the critical concentration of forming a rheological percolation network. Under weak shear, negative normal stress differences(ΔN) are observed in CB, MWNT and graphene suspensions, while ΔN is nearly zero for HCS suspensions. It is concluded that the vorticity alignment of CB, MWNT and graphene agglomerates under shear results in the negative ΔN. However, no obvious structural change is observed in HCS suspension under weak shear, and accordingly, the ΔN is almost zero.     

Rheology of linear and branched styrene–acrylonitrile copolymers. Similarities and differences

A comprehensive investigation of rheological properties of linear and branched styrene-acrylonitrile copolymer specimens with similar molecular characteristics has been carried out. During the steady-state shear flow, the viscosity properties of both specimens are described by the Cross equation. In this case, the branched copolymer is characterized by a higher viscosity and shear thinning degree as well as by substantially lower shear rate values corresponding to transition to the non-Newtonian flow region. The elasticity of the branched copolymer melt (estimated from the value of the first normal stress difference) is considerably higher than that of the linear. This is reflected on the characteristics of occurrence of unstable flow at high shear rates. Rougher extrudate surface distortions are characteristic for the branched copolymer, and the shear rate corresponding to their occurrence is noticeably lower than for the linear copolymer. The dynamic characteristics of the copolymers being compared also attest to a greater elasticity of the branched specimen. An investigation of the viscoelastic properties in a wide temperature range allowed constructing a generalized frequency dependence of dynamic moduli encompassing various regions of the relaxation states of the copolymer specimens. Continuous relaxation spectra were calculated by means of the Mellin transform. It is shown that relaxation phenomena caused by segmental mobility doesn’t depend on the presence of branchings, whereas branching of the chain has a substantial effect on translation mobility of the chain as a whole. Branching leads to a noticeable increase of transient elongation viscosity but has almost no effect of strain hardening of the melt.     

Remarks on the shear viscosity of surfaces stabilised with soluble surfactants

A survey is made of previously reported values of the surface shear viscosity of sodium dodecyl sulphate solution which reveals inconsistencies. The origin of these inconsistencies is thought to be due to the fact that, because SDS is a soluble surfactant, the surface deformation rate is governed by a three-dimensional sublayer adjacent to the surface and is therefore inherently experiment-dependent. Because of this, only an apparent surface shear viscosity that is specific to a particular experiment can be measured. However, for an insoluble surfactant, an intrinsic two-dimensional surface viscosity can be clearly defined. Some methods of measuring an apparent surface shear viscosity assume that the surface shear viscosity is the only surface property that determines the drainage rate from foam or individual Plateau borders but there is experimental evidence to show that other surface properties may be significant.