Mri measurements of T1, T2 and D for gels undergoing volume phase transition

Gels consist of crosslinked polymer network swollen in solvent. The network of flexible long-chain molecules traps the liquid medium they are immersed in. Some gels undergo abrupt volume change, a phase transition process, by swelling-shrinking in response to external stimuli changes in solvent composition, temperature, pH, electric field, etc. We report that during volume phase transition changes of NMR longitudinal relaxation time T(1), NMR transverse relaxation time T(2), and diffusion coefficient D of the PMMA gel, and D of the NIPA gel. We describe how the gels were synthesized and the reason of using the snapshot FLASH imaging sequence to measure T(1), T(2), and D. Since T(1), T(2) and D maps have identical field of view and data are extracted from identical areas from their respective maps, these values can be correlated quantitatively on a pixel-by-pixel basis. Thus a complete set of NMR parameters is measured in-situ: the gels are in their natural state, immersed in the liquid, during the phase transition. The results of spectroscopic method agree with that of snapshot FLASH imaging method. For the PMMA gel T(1), T(2) and D decrease when gels undergo volume phase transition between deuterated acetone concentration of 30% and 40%. At its contracted state, T(1) is reduced to a little less than one order of magnitude, T(2) over two orders of magnitude, and D over one order of magnitude, smaller from values of PMMA gel at the swollen state. At an elevated temperature of 54 degrees C the thermosensitive NIPA gel is at a contracted state, with its D reduced to almost one order of magnitude smaller from that of the swollen NIPA at room temperature.     

Study on the Dynamic Rheometry and Swelling Properties of the Polyacrylamide/Laponite Nanocomposite Hydrogels in Electrolyte Media

Polyacrylamide/laponite/chromium triacetate nanocomposite (NC) hydrogels were prepared by incorporation of the laponite nanoparticles in partially hydrolyzed polyacrylamide followed by cross-linking of their aqueous solutions with chromium triacetate. Influence of nanoparticle, cross-linker, polymer concentrations, and gelation media (water) temperature, salinity, and rheometer frequency on the viscoelastic behavior of the NC hydrogels were studied by probing the network properties. In addition, swelling behaviors of these NC gels in tap and oil reservoir water were evaluated. According to dynamic rheometry of the gelation process, the limiting storage modulus of the NC gels increased with increasing laponite content. The addition of laponite into the polyacrylamide gelling system increased their viscous properties more strongly than the elastic properties. The ultimate elastic modulus of the NC gels increased with increasing water salinity and temperature. Increasing rheometer frequency during gelation retarded the sol–gel transition and decreased the ultimate elastic modulus. The equilibrium swelling ratio of the NC hydrogels in tap water decreased with increasing laponite content. The salt sensitivity of the NC gels in oil reservoir water slightly decreased with increasing laponite content. These results suggest the superiority of the hydrolyzed polyacrylamide (HPAM)/chromium acetate/laponite NC hydrogels for water shut-off applications in oil reservoirs as compared with unfilled HPAM gels.     

Development of high-radiation-sensitive polymer gel for magnetic resonance imaging in three-dimensional dosimetry

We developed a high radiation sensitive polymer gel by modifying the amounts of the gel components and the temperature for the gel preparation. We evaluated its relaxation time linearity against dose and compared the measured dose distribution with the calculated one. For the relaxation time-dose linearity, irradiations were carried out with a linear accelerator using 6 MV photons and doses ranging from 0-5.0 Gy. The relationship between dose and R(2) value (reciprocal of T(2) relaxation time) was measured and it had good linearity over a wide range (0.3-5 Gy). The measured dose distributions were in good agreement with calculated ones. Since the present gel has higher sensitivity and it is synthesized more easily at lower cost than conventional polymer gels, we expect to see improved three-dimensional (3D) dosimetry using it.     

Swelling of cross-linked polyelectrolyte gels

A model of a cross-linked polyelectrolyte gel has been examined using Monte Carlo simulations. The simple model contained a charged defect-free network represented by linked charged beads and explicit counterions. Pressure-density relations for the polyelectrolyte gel, a corresponding non-ionic polymer gel, and several partly or fully degraded gels have been determined. The polyelectrolyte gel displayed a very large swelling capacity, in agreement with experiments. The swelling mechanism and chain properties are discussed and foundations of current theories on gel swelling are examined.     

Shear stress at the interface of coaxial composites determined by the resonance of low-amplitude vibrations

The aim of this work is to determine the viscoelastic behaviour of the interface in a coaxial composite material made of a tough shield and a ductile core. The elastic modulus and the amplitude-independent internal friction are measured using a longitudinal oscillating resonant system at 50 kHz. The contribution of the interface is modelled as a shear stress that modifies the elastic behaviour of the constituents. The value of this shear stress is determined for different interfaces (epoxy resin-brass, epoxy resin-Pyrex and paraffin-Pyrex). The model is autovalidated by the excellent agreement between the calculated and experimental values of the internal friction (damping) of the composites.     

Gelation Rheology and Water Absorption Behavior of Semi-Interpenetrating Polymer Networks of Polyacrylamide and Carboxymethyl Cellulose

Gelation rheology and swelling behavior of novel semi-interpenetrating polymer network (semi-IPN) hydrogels based on polyacrylamide are described. These hydrogels were prepared by solution cross-linking of partially hydrolyzed polyacrylamide and carboxymethyl cellulose (CMC), using chromium triacetate. Effects of CMC content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels increased with increasing CMC content. Enhancement of storage modulus was more than two times for the semi-IPN gels containing 50 wt% CMC. It was also found that increasing the CMC content decreased the loss factor, indicating that the elastic properties of this gelling system increase more strongly than the viscous properties. The swelling ratio of the semi-IPN gels in tap water, NaCl and CaCl₂ solutions, and synthetic oil reservoir water slightly decreased as the concentration of the CMC increased. The improved storage modulus and slightly decreased swelling capacity in oil reservoir water make these semi-IPN hydrogels potentially good candidates for excess water treatment in oil recovery applications.     

Dielectric relaxation spectrum of water studied by the site—site generalized Langevin/modified mode-coupling theory

The dielectric relaxation spectrum of water is calculated from the site-site generalized Langevin/modified mode-coupling theory. The main part of the relaxation follows the Debye-type function, and a small deviation from the Debye relaxation is found on the high-frequency side. This tendency is consistent with recent experiments, although the absolute relaxation time does not agree with the experimental value quantitatively. The time development of the longitudinal polarization function resembles the dielectric part of the memory function, and we consider that this is because the dielectric friction dominates the collective reorientation of the dipole moment of water. We performed calculations with different dielectric constants using the reference interaction-site model integral equation, and found that the large gap between the time scales of the dielectric relaxation and the longitudinal polarization relaxation causes the Debye-type dielectric relaxation in our theory when the dielectric friction is dominant in the friction on the collective reorientation of the dipole moment. Namely, the longitudinal polarization relaxation is fast enough to be considered as a white noise to the dielectric relaxation process, so that the relaxation becomes a Markov process. The large gap between the two relaxation times originates from a large local field correction owing to the large dielectric constant of water. It is also suggested that the deviation from the Debye relaxation at the high-frequency side is the manifestation of the slow memory caused by the long-time part of the longitudinal polarization relaxation in the low-wavenumber region.     

Preparation,Characterization and Coreflood Investigation of Polyacrylamide/Clay Nanocomposite Hydrogel System for Enhanced Oil Recovery

The synthesis and characterization of polyacrylamide/clay nanocomposites for the development of hydrogel system used in enhanced oil recovery is described. The synthesized nanocomposite copolymer was crosslinked with Chromium (III) acetate to form the hydrogel which exhibited an acceptable gel strength, gelation time and gel stability. The nanocomposite gels prepared with low crosslinker concentration (2000 ppm chromium acetate) showed higher gel strength and required longer gelation time than the conventional polyacrylamide (PAAm) gel; these are desirable properties for the effective placement of gel during enhanced oil recovery operations. The effects of various parameters, such as polymer and crosslinker concentration, on the gelation time and gel strength were evaluated using the bottle testing method. X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM) revealed the formation of intercalated and exfoliated clay morphologies. The effects of the clay content on the thermal stability and gel strength of the gel network were also investigated by thermogravimetric analysis (TGA) and rheological measurements (oscillatory time sweep profiles), respectively. Also, in-situ gelation and core flooding experiments revealed that a significant permeability reduction of the sand pack cores could be achieved at reservoir conditions when they were treated with the developed nanocomposite gel formulation. Hence, this nanocomposite gel system with low crosslinker concentration (10,000 ppm of nanocomposite polymer concentration containing 2000 ppm of clay with 2000 ppm chromium acetate crosslinker) may be suitable in water shut-off treatments required for enhanced oil recovery from the oil fields.     

Shear modulus of shock-compressed LY12 aluminium up to melting point

Asymmetric plate impact experiments are conducted on LY12 aluminium alloy in a pressure range of 85-131 GPa. The longitudinal sound speeds axe obtained from the time-resolved particle speed profiles of the specimen measured with Velocity Interferometer System for Any Reflector （VISAR） technique, and they are shown to be good agreement with our previously reported data of this alloy in a pressure range of 20-70 GPa, and also with those of 2024 aluminium reported by McQueen. Using all of the longitudinal speeds and the corresponding bulk speeds calculated from the Gruneisen equation of state （EOS）, shear moduli of LY12 aluminium alloy are obtained. A comparison of the shear moduli in the solid phase region with those estimated from the Steinberg model demonstrate that the latter are systematically lower than the measurements. By re-analysing the pressure effect on the shear modulus, a modified equation is proposed, in which the pressure term of P/η^1/3 in the Steinberg model is replaced by a linear term. Good agreement between experiments and the modified equation is obtained, which implies that the shear modulus of LY12 aluminium varies linearly both with pressure and with temperature throughout the whole solid phase region. On the other hand, shear modulus of aluminium in a solid-liquid mixed phrase region decreases gradually and smoothly, a feature that is very different from the drastic dropping at the melting point under static conditions.     

Shear modulus of shock-compressed LY12 aluminium up to melting point

Asymmetric plate impact experiments are conducted on LY12 aluminium alloy in a pressure range of 85--131\,GPa. The longitudinal sound speeds are obtained from the time-resolved particle speed profiles of the specimen measured with Velocity Interferometer System for Any Reflector (VISAR) technique, and they are shown to be good agreement with our previously reported data of this alloy in a pressure range of 20--70\,GPa, and also with those of 2024 aluminium reported by McQueen. Using all of the longitudinal speeds and the corresponding bulk speeds calculated from the Gruneisen equation of state (EOS), shear moduli of LY12 aluminium alloy are obtained. A comparison of the shear moduli in the solid phase region with those estimated from the Steinberg model demonstrate that the latter are systematically lower than the measurements. By re-analysing the pressure effect on the shear modulus, a modified equation is proposed, in which the pressure term of $P/\eta^{1/3}$ in the Steinberg model is replaced by a linear term. Good agreement between experiments and the modified equation is obtained, which implies that the shear modulus of LY12 aluminium varies linearly both with pressure and with temperature throughout the whole solid phase region. On the other hand, shear modulus of aluminium in a solid-liquid mixed phrase region decreases gradually and smoothly, a feature that is very different from the drastic dropping at the melting point under static conditions.     

Phase transition in polymer gels due to local heating by illumination of light

The volume phase transition in gels induced by visible light and its related properties are presented, the mechanism of which is based on local heating of a polymer network by illumination of light. The gels consist of a covalently cross-linked copolymer network of thermosensitive N-isopropylacrylamide and a chromophore. Without light illumination, the gel volume changes sharply, but continuously at approximately 34°C when the temperature is varied. At a fixed temperature of an appropriate value, a discontinuous volume transition is observed when the light intensity is gradually changed. The phase transitions can be understood in terms of the temperature increment at the immediate vicinity of polymer chains due to the local heating via light absorption and subsequent thermal dissipation of light by the chromophore. The results can be qualitatively described by the Flory-Huggins mean-field equation of state of gels. In order to make clear the mechanism of the light-induced phase transition in the present system, we measured the light transmitting properties and the swelling as well as shrinking kinetics. These preliminary results are described semi-qualitatively by making use of a simple phenomenological model.     

Acoustic study of the elastic and inelastic properties of high-pressure polyethylene samples with different irradiation histories

The influence of vibrational deformation amplitude ε on the dynamic elasticity modulus (Young’s modulus E) and internal friction (logarithmic decrement δ) of high-pressure polyethylene samples with different histories is studied. Acoustic measurements are made by a resonance method using the longitudinal vibrations of a composite piezoelectric vibrator at a frequency of ≈ 100 kHz. The dependences E(ε) and δ(ε) are taken at room temperature. From the acoustic data, the elasticity and microplasticity of the samples are estimated. It is found that the microplasticity remains almost unaffected upon irradiation and aging, while the elasticity modulus and breaking elongation per unit length considerably depend on the history and clearly correlated with each other. The observed effects are explained by the fact that atom-atom interaction and defects inside polymer macromolecules substantially influence the elastic modulus and breaking strength, while the inelastic microplastic strain is most likely associated with molecule-molecule interaction, which is affected by irradiation insignificantly.     

Effect of ultrasonic pretreatment on the rheology and structure of grass pea (Lathyrus sativus L.) protein emulsion gels induced by transglutaminase

In this study, emulsion gels were prepared by sonicated grass pea protein isolates (GPPI) at different ultrasonic amplitudes (25, 50 and 75 %) and times (5, 10 and 20 min). Formation of emulsion gels was induced by transglutaminase. Enzymatic gelation of emulsions stabilized by sonicated GPPI occurred in two stages. A relatively fast stage led to the formation of a weak gel which was followed by a slow stage that strongly reinforced the gel structure. Emulsion gels fabricated by sonicated GPPIs showed a homogeneous and uniform droplet distribution with higher elastic modulus compared to the native protein. A stiffer emulsion gel with a higher G' was formed after the protein was treated at 75 % amplitude for 10 min. After sonication of GPPI, the water holding capacity (WHC) of emulsion gels increased in accordance with the mechanical properties. Higher intermolecular cross-linking within the gel network increased the thermal stability of emulsion gels fabricated by sonicated GPPI. Although sonicated-GPPI emulsion gels clearly displayed homogenous microstructure in comparison to that made with native GPPI, the microstructures of these gels were nearly identical for all sonication amplitudes and times.     

Nonlinear shoaling of shallow water waves: perspective in terms of the inverse scattering transform

Summary We study nonlinear interactions in measured surface wave trains obtained in the Northern Adriatic Sea about 16 kilometres from Venice, Italy.Nonlinear Fourier analysis is discussed in terms of the exact spectral solution to the Korteweg-deVries (KdV) equation as given by theinverse scattering transform (IST). For the periodic and/or quasi-periodic boundary conditions assumed herein, the approach may be viewed as a nonlinear, broad-banded generalization of the ordinary, linear Fourier transform. In particular, we study solition interactions, their properties and the nonlinear dynamics of the radiation (or oscillation) modes as found from the inverse scattering transform analysis. We also conduct a number of computer experiments in which measured wave trains are numerically propagated forward in time toward shallow water and backward in time into deep water in order to assess how the nonlinear wave dynamics are influenced by propagation over variable bathymetry. On this basis we develop a scenario for the evolution of nonlinear wave trains, initially far offshore in deep water, as they propagate into shallow water regions. The deep-water waves have a small Ursell number and are hence not very nonlinear; as they propagate toward shallow water, the Ursell number gradually increases in the numerical experiments by about an order of magnitude. A useful parameterization of nonlinearity in these studies is the ?spectral modulus,? a number between 0 and 1, which is associated with each IST spectral frequency. Small values of the modulus mean that a particular spectral component is linear (a sine wave); large values of the modulus (≈1) indicate that the component is nonlinear (a soliton). There is a systematic increase of the modulus as the waves propagate into shallow water where nonlinear effects predominate; we describe how the modulus varies as a function of spectral frequency during this shoaling process. The results suggest that the effect of increasing nonlinearity ?saturates? the IST spectrum (i.e. the modulus ≈1 for all frequencies) to that virtually all spectral components become solitons in sufficiently shallow water.     

Investigation of biopolymer networks by means of AFM

Natural hydrogel alginate was investigated by means of atomic force microscopy (AFM) to gain microscale information on the morphological and rheological properties of the biopolymer network cross-linked by various cations. Local rheological properties of the gels measured by force spectroscopy gave correlation between increasing ion selectivity and increasing polymer elasticity. Adhesive forces acting between the surface of the gel and the probe, and also the intrinsic rheological properties of bulk polymers affect the microscopical image formation.     

水平环道内油水气多相流动研究

为建立自主的多相流动数据库,在水平环道中进行了一系列水－气两相、油－气两相和油－水－气三相流动试验。本文测量了各相流动中由于摩擦而产生的压力损失,计算了压差梯度并作了比较;观察了各相流动中的流型;描述了各种流型的发生、发展和变化及其与流动介质的关系,并作了相互比较。     

Polyelectrolyte gels in poor solvent: Elastic moduli

We study theoretically using scaling arguments the behavior of polyelectrolyte gels in poor solvents. Following the classical picture of Katchalsky, our approach is based on single-chain elasticity but it accounts for the recently proposed pearl necklace structure of polyelectrolytes in poor solvents. The elasticity both of gels at swelling equilibrium and of partially swollen gels is studied when parameters such as the ionic strength or the fraction of charged monomers are varied. Our theory could be useful to interpret recent experiments performed in Strasbourg that show that if identical gel samples are swollen to the same extent at different pH the sample with the highest charge has the lowest shear modulus. Received 7 April 2000     

Rheology of nanosized hairy grain suspensions

Suspensions of nanosized hairy grains have been prepared by grafting long polydimethylsiloxane chains (molecular weight ) onto silica particles (radius ), dispersed into a good solvent of PDMS. Depending on the particle volume fraction, different rheological behaviors are observed. In the very dilute regime, the suspensions are perfectly stable and the particles behave almost as hard spheres: flow penetration inside the corona is then very weak. When the particle volume fraction goes to the close packing volume fraction, the suspension viscosity does not diverge as for hard spheres due to the increase of flow penetration inside the corona and to corona entanglements. The particles have then the same behavior as polymer stars having an intermediate number of arms (). Finally, in the concentrated regime (), the suspensions form irreversible gels. We shown that this unexpected gelation phenomenon is related to the presence of the silica cores: grafted PDMS chains can adsorb onto different particles and form irreversible bonds between the cores. The viscosity and elastic modulus evolutions during gelation are well described by the scalar percolation model of sol-gel transition. Received 23 March 1998     

Studies on mechanical and swelling behavior of polymer networks on the basis of the scaling concept. 6. Gels immersed in polymer solutions

In order to describe the mechanical and swelling behavior of gels immersed in polymer solutions, theoretical considerations based on both classical and scaling theories are discussed and compared with experimental findings. Three situations are studied: (1) the gel is separated from the surrounding solution by a semipermeable membrane; (2) the gel is immersed in the semidilute solution of a chemically identical polymer; (3) the gel is directly immersed in the semidilute solution of a chemically different polymer. An attempt is made to take into account the effect of the penetrating polymer on the elastic modulus and the swelling pressure of the gel. Experimental data referring to chemically cross-linked poly(vinyl alcohol) and poly(vinyl acetate) networks are presented. It was found that the concentration of the free chains inside moderately cross-linked networks may be considerable even for polymers having relatively long chains (27,000 < < M _n < 130,000). Experimental results indicate that the presence of free chains only slightly alters the elastic modulus; however, the swelling pressure is considerably affected by the penetrating polymer. The analysis of mechanical and equilibrium deswelling measurements carried out on several series of gel homologues shows that scaling theory satisfactorily describes the experimental data.     

Preparation and Swelling Behavior of Partially Hydrolyzed Polyacrylamide Nanocomposite Hydrogels in Electrolyte Solutions

In this research, nanocomposite hydrogels were prepared by cross‐linking of partially hydrolyzed polyacrylamide/sodium montmorillonite aqueous solutions with chromium triacetate. The gelation process and influence of nanoclay content and salt concentration on swelling behavior were investigated. Study of gelation behavior using dynamic rheometry method showed that increasing the nanoclay content decreases the storage modulus, due to the partial adsorption of polymer chains onto the clay surface and ionic interaction between negative layers of sodium montmorillonite and Cr.³⁺ By increasing the cross‐linker concentration of the gelation system, the viscous energy dissipation properties of the nanocomposite gel decreases. Swelling ratio of the nanocomposite gels in distilled water decreased as the concentration of the nanoclay increased. However, nanocomposite gels showed lower salt sensitivity in electrolyte media compared with unfilled gels.