Static and time-dependent properties of polymer gels around the volume phase transition

Recent progress in the study of the volume phase transition of polymer gels is reviewed. The phenomenological theories of swelling equilibrium and phase transition of gels are summarized, and some basic experimental results on poly-N-isopropylacrylamide (NIPA) gels are compared with the prediction from these theories. Special attention is paid to the elastic properties of the gel network near the volume phase transition. The effect of external stresses on the swelling and the phase transition is analyzed. Some anomalous and unique characteristics revealed in NIPA gels such as shape- and size-dependent swelling and phase transition properties, curious phase coexistence, and domain structure are presented. Experimental results on some time-dependent phenomena such as phase separation, spinodal decomposition, and pattern formation are also presented and discussed. Some problems inherent to gels from biological bodies are briefly discussed.     

海藻酸钠/大豆蛋白共混凝胶微球的结构

利用钙离子交联海藻酸钠／大豆分离蛋白共混溶液，制得海藻酸钠／大豆分离蛋共混凝胶微球．结果表明，海藻酸钠和大豆分离蛋白质量配比的不同以及各组分间相互作用的变化，微球呈现不同的微观结构．将微球干燥后置于水中溶胀，微球的尺寸无法回复到干燥前的尺寸，这是由于真空干燥处理使水分子挥发，促进微球内组分间形成了强的氢键作用所致．此外，用碱处理该共混微球，发现由于大豆分离蛋白溶解以及部分钙离子被置换析出，微球塌陷且内部形成了大孔．     

Strongly localized states in a single carbon nanotube with polymer molecules

A single-walled carbon nanotube (SWCNT) with conjugated polymer molecules is analyzed via optical spectroscopy. The presence of strongly localized excitonic states in the SWCNT is confirmed using time-integrated photoluminescence (PL). The PL spectrum exhibits extremely narrow width (~0.8 meV) which is attributed to the strong confinement of the states by polymer molecules. In addition, I observed that the excited states are gradually filled as a function of the excitation power, which supports the localized excitonic behavior. Only the ground excitonic state is observed at low excitation powers, but three additional PL peaks appear as the excitation power is increased. Especially, the power-dependent PL spectrum shows a blueshift and increased width, which can be elucidated in terms of quantum confined stark effect and the screening of induced electric fields. Overall, I demonstrate that the presence of polymer molecules induces several localized states in a single SWCNT.     

Restoration of universality for the rod-to-coil transition scaling in the infinite-dimensionality limit: Exact results for directed walks

We derive scaling forms for the thermodynamic and correlation quantities for the turn-weighted fully and partially directed self-avoiding walks on the hypercubic lattices ind2. In the grand canonical (fixed fugacity per step) ensemble, the conformational rod-to-coil transition sets up in the regimew¯N=O(1), wherew is the weight of each 90° turn and¯N is the (fugacity-dependent) average number of steps. Contrary to the conventional critical phenomena wisdom, the scaling functions for the two different walk models, directed and partially directed, become universal only in the limitd.     

A three-parameter model describing the experimental relation between shear stress and shear rate for laminar flow of aqueous polymer solutions

Summary A three-parameter model is introduced to describe the shear rate — shear stress relation for dilute aqueous solutions of polyacrylamide (Separan AP-30) or polyethylenoxide (Polyox WSR-301) in the concentration range 50 wppm – 10,000 wppm. Solutions of both polymers show for a similar rheological behaviour. This behaviour can be described by an equation having three parameters i.e. zero-shear viscosity ₀, infinite-shear viscosity , and yield stress ₀, each depending on the polymer concentration. A good agreement is found between the values calculated with this three-parameter model and the experimental results obtained with a cone-and-plate rheogoniometer and those determined with a capillary-tube rheometer.

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Zusammenfassung Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit von strukturviskosen Flüssigkeiten wird durch ein Modell mit drei Parametern beschrieben. Mit verdünnten wäßrigen Polyacrylamid-(Separan AP-30) sowie Polyäthylenoxidlösungen (Polyox WSR-301) wird das Modell experimentell geprüft. Beide Polymerlösungen zeigen im untersuchten Schergeschwindigkeitsbereich von ein ähnliches rheologisches Verhalten. Dieses Verhalten kann mit drei konzentrationsabhängigen Größen, nämlich einer Null-Viskosität ₀, einer Grenz-Viskosität und einer Fließgrenze ₀ beschrieben werden. Die Ergebnisse von Experimenten mit einem Kegel-Platte-Rheogoniometer sowie einem Kapillarviskosimeter sind in guter Übereinstimmung mit den Werten, die mit dem Drei-Parameter-Modell berechnet worden sind.

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a Pa^–1 physical quantity defined by:a = {1 – ( / ₀)}/ ₀ - c l concentration (wppm) - D m capillary diameter - L m length of capillary tube - P Pa pressure drop - R m radius of capillary tube - u m s^–1 average velocity - v _r m s^–1 local axial velocity at a distancer from the axis of the tube - shear rate (–dv _r /dr) - local shear rate in capillary flow - s^–1 wall shear rate in capillary flow - Pa s dynamic viscosity - _a Pa s apparent viscosity defined by eq. [2] - ( _a ) Pa s apparent viscosity in capillary tube at a distanceR from the axis - ₀ Pa s zero-shear viscosity defined by eq. [4] - Pa s infinite-shear viscosity defined by eq. [5] - l ratior/R - kg m^– density - Pa shear stress - ₀ Pa yield stress - _r Pa local shear stress in capillary flow - _R Pa wall shear stress in capillary flow _R = (PR/2L) - _v m³ s^–1 volume rate of flow With 8 figures and 1 table     

The rheology of suspensions of vinylon fibers in polymer liquids. II. Suspensions in polymer solutions

Summary The rheological properties of vinylon fiber suspensions in polymer solutions were studied in steady shear flow. Shear viscosity, first normal-stress difference, yield stress, relative viscosity, and other properties were discussed. Three kinds of flexible vinylon fibers of uniform length and three kinds of polymer solutions as mediums which exhibited remarkable non-Newtonian behaviors were employed. The shear viscosity and relative viscosity ( _r ) increased with the fiber content and the aspect ratio, and depended upon the shear rate. Shear rate dependence of _r was found only in the low shear rate region. This result was different from that of vinylon fiber suspensions in Newtonian fluids. The first normal-stress difference increased at first slightly with increasing fiber content but rather decreased and showed lower values for high content suspensions than that of the medium. A yield stress could be determined by using a modified equation of Casson type. The flow properties of the fiber suspensions depended on the viscosity of the medium in the suspensions under consideration.With 16 figures and 1 table     

On the theory of the condensed states of heteropolymers

The collapse (globulization) of an ideal heteropolymer chain under the action of an external attractive field is considered. The problem of the collapse of different types of primary structures, including mobile, periodic, large-block, and statistical structures, is formulated. It is shown that for a random heteropolymer, the mathematical image of the globular state is the chain-length independence of the probability distribution of a random thermal distribution function of the end monomer coordinates. The free energy per monomer of a chain in a globular state and local densities of monomers of all types are shown to be a self-averaging quantities. An exactly solvable model is proposed for a globule formed by a statistical heteropolymer chain. In this model, different types of monomers are attracted to different centers by linear elastic forces with identical elastic constants. The modulus of elasticity is obtained for a heteropolymer globule with respect to the attraction of different types of monomers in different directions. It is shown that this modulus is higher for a short-periodic polymer than for a statistical one.     

Fabrication of polymer compound microlens by lens-on-lens microstructures

We proposed a novel method for fabricating polymer compound microlenses (PCMLs) using micro-inkjet technique and subsequent curing process. Two different types of PCMLs with sandwich microstructure (PDMS-Glycerol-PDMS), concave and convex PCMLs, have been designed and fabricated in experiments. Convex PCML has two real images and two foci. The concave PCML has one real and one virtual focal planes, which can generate one real image and one virtual image respectively. Moreover, the diameter of concave PCML can be controlled by adjusting the curing time and temperature. The proposed method is simple, efficient and suitable for realizing large-scale high numerical aperture PCMLs array, which has potential applications in diverse optical systems such as optical storage and three-dimensional imaging.     

Synthesis and Properties of Cupric Sulphate Doped Polyvinyl Pyrrolidone (PVP) Solutions

The optical, electrical and acoustical properties of polymer solutions based on polyvinyl pyrrolidone (PVP) doped with cupric sulphate (CuSO₄) were studied. The polymer solutions were prepared by varying the concentration of Cu in the PVP using a simple chemical route. The UV-visible spectroscopy results showed that the optical absorbance decreased with an increase in wavelength from 300 to 700 nm. The optical band gaps were found to decrease with addition of the Cu salt in the polymer. The refractive index also showed significant variation with the doping of the CuSO₄. The electrical conductivity of the polymer solutions was found to increase with temperature as well as concentration of Cu while the activation energy of electrical conduction decreased with concentration of Cu. The ultrasonic velocities of the polymer solutions were measured at a frequency of 1 MHz using an ultrasonic interferometer. The ultrasonic velocity and surface tension were increased while the adiabatic compressibility, acoustic impedance and intermolecular free length, the average distance between the surfaces of the coils of adjacent molecules, were decreased with increase in the concentration of CuSO₄ in the PVP.     

Optimized analysis of the critical behavior in polymer mixtures from Monte Carlo simulations

A complete outline is given for how to determine the critical properties of polymer mixtures with extrapolation methods similar to the Ferrenberg-Swendsen techniques recently devised for spin systems. By measuring not only averages but the whole distribution of the quantities of interest, it is possible to extrapolate the data obtained in only a few simulations nearT _c over the entire critical region, thereby saving at least 90% of the computer time normally needed to locate susceptibility peaks or cumulant intersections and still getting more precise results. A complete picture of the critical properties of polymer mixtures in the thermodynamic limit is then obtained with finite-size scaling functions. Since the amount of information extracted from a simulation in this way is drastically increased as compared to conventional methods, the investigation of mixtures with long chains or built-in asymmetries is now possible. As an example, the critical points, exponents, and amplitudes of dense, symmetric polymer mixtures with chain lengths ranging fromN=16 up toN=256 are determined within the framework of the 3D bond fluctuation model using grand canonical simulation techniques. As an example for an asymmetry, the generalization of the method to asymmetric monomer potentials is briefly discussed.