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.     

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.     

Temperature-responsive poly(N-isopropylacrylamide) gels containing polymeric surfactants

Poly(N-isopropylacrylamide) (PNIPA) gel containing polymer surfactant poly(2-(methacryloyloxyl)decylphosphate) (PMDP) was synthesized and was found to show rapid volume phase transition above its transition temperature. Interestingly, the phase transition temperature of the PNIPA–PMDP gel was equal to that of the PNIPA gels alone. The concentration gradient of PMDP within the PNIPA gel can be obtained by applying an electric field on the gel, similar to the gel electrophoretic technique. The PMDP-gradient PNIPA gel clearly demonstrated the prevention of skin formation and the acceleration of the phase transition rate of the PNIPA gel by PMDP. The rapid volume phase transition allows potential applications of the PNPA–PMDP gel to soft actuators and drug delivery systems. Recently we also succeeded in synthesizing cylindrical microgels (0.8 μm in diameter, 5 μm in length) by a novel strategy where template-guiding synthesis and photochemical polymerization are combined. The obtained microgels can be characterized in individual level by a laser-trapping/Raman spectroscopy. In this article we also briefly described a famous gel system containing ionic surfactant capable of electrically driven actuators although it is not PNIPA gel.     

高分子凝胶体积相变中的氢键作用

我们把关联模型(association models)推广应用到高分子凝胶体系,研究高分子与溶剂分子间的氢键和溶剂分子与溶剂分子间的氢键在高分子凝胶体积相变中的作用.首先通过分析凝胶体积分数与温度的关系发现,由于两种氢键作用,随着温度变化高分子凝胶出现连续、不连续体积相变,结果表明在体积相变过程中两种氢键都起着重要作用.其次,对不同氢键分数条件下的旋节线的研究发现,对于高分子凝胶体积相变中出现的UCST和LCST(上临界共溶温度和下临界共溶温度)现象也是由于高分子与溶剂分子间氢键和溶剂分子与溶剂分子间氢键共同作用的结果.     

一种共轭聚合物单分子发色团吸收和发射特性动态演变过程的实时测量

利用频域信息重构的散焦宽场成像测量了Poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子发色团的吸收与发射特性及其动态演变过程.通过调制用于激发共轭聚合物单分子的超短脉冲对的相对相位,对单分子荧光进行傅里叶变换的频域测量,跟踪发色团吸收偶极取向变化;通过测量散焦荧光成像光斑探测发色团发射偶极取向变化.研究发现, PFO-DBT共轭聚合物单分子发色团存在吸收和发射偶极取向均保持不变、其中之一变化以及两者同时变化三种情况.这种对共轭聚合物单分子发色团吸收和发射偶极取向演化过程的实时测量可用于分析共轭聚合物构象变化及其对能量转移过程的影响.     

Reversible light-induced capacitance switching of azobenzene ether/PMMA blends

Fully reversible light-induced switching of the capacitance with changes larger than 50% has been achieved by using photo-active thin polymer films. The films consist of PMMA polymer blended with high concentrations of branched azobenzene ether dye molecules. Polymer thin sheet capacitors can be easily produced by spin coating and drop casting in various thicknesses ranging from 100 nm to 8 μm, respectively. Reversible capacitance switching is induced by illumination with UV and visible light, respectively. The capacitance change is correlated to the trans to cis isomerization of the azobenzene ether molecules and the alignment of the molecular dipoles in the film. Switching times depend on chromophore concentration, film thickness and light intensity used. The influence of wavelength of the light, of the temperature as well as of an electrical field applied during illumination on the capacitance change is addressed.     

Thermo-sensitive N-n-propylacrylamide gels

Thermo-sensitive gels were prepared by irradiating aqueous solutions of poly(N-n-propylacrylamide) (NNPA) and its copolymers with acrylic acid (AA) with γ-rays from a ⁶⁰Co source. The equilibrium swelling volume of the gel in water was determined as a function of temperature. NNPA gel showed a discontinuous and reversible volume phase transition. The transition temperature and the volume change at the transition decreased with irradiation time. The transition temperature was approximately 12°C lower than that of poly(N-isopropylacrylamide) gel. A discontinuous volume transition was also observed in the copolymer gels of NNPA and AA. The dependence of the transition temperature on the concentration of carboxyl groups revealed a marked difference depending on whether they were protonated or dissociated. For gels having side groups of COONa, the transition temperature rose and the volume change at the transition was elevated as the COONa concentration increased. In contrast, an increase in the COOH concentration resulted in a decrease in the transition temperature. These results are discussed in terms of an equation of state constructed based on scaling theory.     

Thermal Phase Transitions of IOTA Carrageenan in CaCl2 Solutions: A Fluorescence Study

The fluorescence technique was employed to study thermal phase transitions of iota (ι-) carrageenan (IC) in CaCl₂ solution. IC gels underwent coil to double helix (c-h) and double helix to dimer (h-d) transitions upon cooling. Upon heating IC gels presented dimer to double helix (d-h) and double helix to coil (h-c) transitions, showing hysteresis types of transition paths. Scattered light, I_sc and fluorescence intensity, I, were monitored against temperature to determine phase transitions. Transition temperatures were determined from the derivative of the transition paths. The critical gel fraction exponent, β, was measured and found to be in accord with the classic Flory–Stockmayer model.     

Thermal Phase Transitions of Agarose in Various Compositions: A Fluorescence Study

The effect of agarose content on thermal phase transitions of the agarose gels was investigated by using Steady State Fluorescence (SSF) method. Scattered light, I _sc and fluorescence intensity, I _fl were monitored against temperature during heating and cooling processes to investigate phase transitions. Two regions were observed during the heating and cooling processes. At the high temperature region, double helix to coil (h-c) transition took place. However, during the cooling process coil to double helix (c-h) transitions occurred at low temperature region. Transition energies were determined using the Arrhenius treatment, and found to be strongly correlated with the agarose content in the gel system. Transition temperatures were determined from the derivative of the sigmoidal transition paths and found to be increased by increasing agarose content in both cases.     

Active Brownian motion tunable by light

Active Brownian particles are capable of taking up energy from their environment and converting it into directed motion; examples range from chemotactic cells and bacteria to artificial micro-swimmers. We have recently demonstrated that Janus particles, i.e.?gold-capped colloidal spheres, suspended in a critical binary liquid mixture perform active Brownian motion when illuminated by light. In this paper, we investigate in more detail their swimming mechanism, leading to active Brownian motion. We show that the illumination-borne heating induces a local asymmetric demixing of the binary mixture, generating a spatial chemical concentration gradient which is responsible for the particle's self-diffusiophoretic motion. We study this effect as a function of the functionalization of the gold cap, the particle size and the illumination intensity: the functionalization determines what component of the binary mixture is preferentially adsorbed at the cap and the swimming direction (towards or away from the cap); the particle size determines the rotational diffusion and, therefore, the random reorientation of the particle; and the intensity tunes the strength of the heating and, therefore, of the motion. Finally, we harness this dependence of the swimming strength on the illumination intensity to investigate the behavior of a micro-swimmer in a spatial light gradient, where its swimming properties are space-dependent.     

偶氮苯侧链聚合物液晶薄膜的光致双折射和永久光学性存储研究

研究了一种含偶氮基侧链聚合物液晶薄膜,该液晶薄膜表现出显着的光致双折射(Δn～1.1×10^-2).当关闭写光作用后,光致双折射的大小没有任何衰减,表现出永久光存储特性.光致双折射的擦除可通过将样品加热到接近其清亮点温度,或用一束圆偏振光照射来实现.分析了偶氮侧链聚合物永久性光学存储的物理机制.     

SMMA/SMA共聚物共混物的自由体积的热动态特性与相分离行为的PALS研究

基于自由体积理论，利用正电子湮灭寿命谱仪(PALS)分别研究在不同升温速率条件下，聚苯乙烯-甲基丙烯酸甲酯共聚物(SMMA)和聚苯乙烯-马来酸酐共聚物(SMA)混合物(30/70)的自由体积参数的温度依赖性，探索相容共混物相行为的热动态特性.在PALS实验中，在玻璃化转变温度T_g以上，当结构松弛的弛豫时间与等温停留时间相当，发现在某一段温度范围内，共混物的自由体积参数随着温度的变化明显地偏离线性关系.从自由体积孔的浓度I₃值在该段的变化趋势，初步推断共混物在该温 关键词： 正电子湮没 正电子素 聚合物共混物 相分离     

Structural transition and metallization in liquid selenium

The insulator-metal transitions of different kinds caused by heating above the melting temperature under pressure of tens kilobars and by compressing at the critical temperature to a pressure of about 1.1 kbar occur in liquid selenium. At tens kilobars, metallization is interpreted as the forbidden energy band vanishing due to a gradual structural transition (melting of polymer chains) described by the Clapeyron-Clausius equation. At supercritical temperatures, the insulator-metal transition is caused by percolation of overlapping electron shells (classically accessible spheres) of virtual atoms in molecules Se₂ remaining when polymer chains decay. The percolation threshold in such a system has been found to increase due to coupling of virtual atoms. The thermally activated conductivity in the vicinity of percolation threshold has been calculated and compared with existing experimental data.     

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.     

Investigation of thermal and deformation properties of quartzite in a temperature range of polymorphous α-β transition by neutron diffraction and acoustic emission methods

The results of combined application of the neutron diffraction and acoustic emission methods for investigation of the physical properties of synthetic quartz and natural quartzite in a temperature range of α-β transition are given. In experiments, the quartzite sample was exposed to heating and uniaxial compression. Changes of the lattice spacings in quartzite were measured in a temperature range 540–620°C. On the basis of these measurements, the inner inner stresses are evaluated and found to exceed the applied stresses by several times. It is found that after the phase transition is finished, short bursts of acoustic emission (AE) occur which are two orders of magnitude more intense than the acoustic emissions produced by thermal cracking of the sample while the sample is heating up to the transition temperatures. An assumption is made that the anomalous behavior of the physical properties of quartz-containing rocks under relatively low pressures near the transition temperature can cause the formation of strong concentrators of local stresses comparable with the breaking point of the material, thereby initiating microcracking.     

电场诱导二氧化钒绝缘-金属相变的研究进展

二氧化钒(VO_2)是电子强关联体系的典型代表,其晶体结构在特定阈值的温度、电场、光照和压力等物理场作用下会发生由单斜金红石结构向四方金红石结构的可逆转变,从而引发绝缘-金属相变.其中,电场诱导VO_2绝缘-金属相变后的电导率可提高2-5个数量级,在可重构缝隙天线、太赫兹辐射以及智能电磁防护材料等领域具有广阔的应用前景,成为近年来人们的研究热点.首先,简要概述了VO_2发生绝缘-金属相变时晶体结构和能带结构的变化,进而从电场诱导VO_2绝缘-金属相变的研究方法、响应时间、临界阈值场强调控以及相变机理几个方面系统总结和评述了近年来国内外学者在该领域的重要发现和研究进展.最后,指出了当前VO_2绝缘-金属相变研究存在的问题,并展望了未来的发展方向.     

Evolution of the optical properties of Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) solid solution single crystals caused by a static electric field

The electric-field-induced variation of the optical properties (small-angle light scattering, birefringence) of PBSN-6 solid solutions was studied. It was found that in the absence of an electric field, the cubic nonpolar matrix contains, at temperatures below the dielectric permittivity maximum, spontaneously polarized regions of the ferroelectric phase not less than 10⁴ Å in size. It was shown that a weak electric field (～0.4 kV/cm) is capable of inducing a kinetic phase transition to the ferroelectric state, with the temperature of this transformation depending on the sample heating rate. The destruction of the induced state was accompanied by a sharp peak in the temperature dependence of the small-angle light scattering intensity (indicating the percolation nature of the transition) and was independent of the sample heating rate. The boundaries of stability of the induced state in various modes of application of an external electric field were determined, and the E-T phase diagram was constructed.     

Freedericksz transition in polymer-stabilized nematic liquid crystals

We have constructed polymer-stabilized nematic liquid crystals by photopolymerizing diacrylate monomers in the nematic phase. The orientation of the liquid crystal was controlled by the polymer network. We studied the Freedericksz transition in these systems. Experimentally we studied the transition by measuring the capacitance of the liquid crystal cells as a function of applied voltage. The transition was affected profoundly by the dispersed polymer network. The threshold was higher with shorter interpolymer network distance. Theoretically we studied the systems using a two-dimensional model in which the polymer networks were represented by parallel cylinders with random location. The interaction between the liquid crystal and the polymer network was described by the boundary condition imposed by the polymer network. By fitting the experimental data, we found that the polymer cylinders had diameters of a few submicrons, and a substantial amount of liquid crystal was trapped inside the cylinders.     

Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions

Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices.