水凝胶体系交联过程织构变化的流变学研究

研究了由部分水解聚丙烯酰胺水溶液交联得到的用于三次采油的弱凝胶体系, 使用不同交联剂的水凝胶体系表现出不同的流变特性, 反映两种不同织态结构的弱凝胶, 一种为接近于均匀分形交联网的整体凝胶, 另一种为有特征尺度的非均匀交联网的胶态分散凝胶. 上述结果得到了光学显微镜观测的证明. 强剪切和拉伸流的结果表明, 当凝胶体系中存在大量胶团时, 强剪切可以加强体系中网络结构的完整性, 使得流变性质加强, 不同于一般凝胶的减弱趋势.     

智能型水凝胶

智能型水凝胶是一类具有广泛应用前景的功能高分子材料，但由于传统水凝胶存在一些缺点因而限制了其应用，因此近年来围绕提高传统水凝胶的性能做了大量研究工作。本文从四个主要方面综述了近年来智能型水凝胶改性的研究进展。     

部分水解聚丙烯酰胺弱凝胶交联动力学的流变学分析

用流变学方法对部分水解聚丙烯酰胺(HPAM)苯酚甲醛间苯二酚交联体系的弱凝胶化过程进行了研究,通过对基团转化率和高分子交联转化率的分析,发现凝胶化过程在接近凝胶点时,处于反应动力学的初期,这使得交联点增加的动力学是比较简单的.通过在不同聚合物浓度和交联剂浓度并在地层温度和矿化度条件下线性粘弹性行为的研究,得到了交联体系凝胶化动力学过程的完整数据,发现聚合物浓度与交联剂浓度对凝胶点与凝胶强度的影响比较类似,反映出交联点增加的共同动力学特征.复数粘度在一个诱导期后,是以指数上升的,类似一个一级反应的特征.产生交联的临界聚合物浓度约为250mg/L左右.并提出了剪切粘度数学模型,可以描述凝胶化过程中流变性质的变化.     

智能性水凝胶

“智能”材料具有传感、处理和执行功能，水凝胶作为智能材料其应用前景良好。本文综述了智能水凝胶的近期研究发展，以Ｆｌｏｒｙ的溶胀理论着重探讨了刺激响应性，并介绍了化学机械现象及凝胶相转变。     

羧甲基纤维素水凝胶生物降解动力学研究

用氯化铝对羧甲基纤维素进行交联,制得了水凝胶.考察了底物浓度、酶浓度以及降解温度对该水凝胶降解速率的影响,探讨了酶降解动力学及“表观”活化能对酶浓度的依赖关系.结果表明,该酶促反应最佳温度为37 ℃,降解反应对底物浓度和酶浓度的反应级数分别为1级和1.2级;得到了与传统的Michaelis-Menten动力学机制不同的非均相酶促反应动力学模型,确定了“表观”活化能与酶浓度之间的定量关系.     

水凝胶功能改性研究与应用进展

水凝胶是一种三维网状亲水性高分子软材料,具有良好的固体力学和液体热力学性能,其自身柔软、可塑性强、生物相容性好,具有可降解性和刺激性响应特征。但传统方法制备的水凝胶有诸多缺陷,如有毒性、生物活性低、机械性能差等,使得其应用受限。本文综述了近10年来功能水凝胶制备与改性的主要研究进展及其应用现状,以多吸收位点和高机械强度等性能为主,重点阐述了国内外功能性水凝胶的最新制备方法,包括物理改性中的低分子复合材料交联与构建多重网络和化学改性中的接枝共聚等。详细介绍了该类功能材料在医药、生物、农业和食品等方面的应用现状与发展前景,特别关注了高效短时对外界环境微小变化具有响性的智能印迹水凝胶及其在检测领域的应用,为水凝胶的进一步开发和推广应用提供参考。     

PAC与PAC/HPMC水凝胶的结构及溶胀规律研究

制备了PAC与一系列PAC/HPMC水凝胶,并研究了这两类水凝胶的动态流变性。通过扫描电镜观察了其形态、结构,并进行了对比分析;在此基础上,考察了PAC与PAC/HPMC凝胶的溶胀动力学,探讨了PAC与PAC/HPMC水凝胶的溶胀机理。结果表明:冷冻干燥后的纯PAC水凝胶内部具有浅而封闭的孔洞,骨架结构较规则。而PAC/HPMC水凝胶凝胶骨架多褶皱、孔洞互穿。并且HPMC的黏度越大,凝胶的孔洞结构越复杂,孔洞贯穿现象越明显;PAC/HPMC凝胶的平衡溶胀率和溶胀速率均大于纯PAC凝胶;随着HPMC黏度增大,PAC/HPMC凝胶的平衡溶胀率也增大。在所研究的范围内,HPMC的用量对PAC/HPMC凝胶的溶胀速率和平衡溶胀率影响不显著;PAC凝胶的溶胀机理属于水分子的Fickian扩散过程,而PAC/HPMC凝胶的溶胀机理属于非Fickian扩散,HPMC的分子链松弛在其中起着不容忽视的作用。     

草酸对非对称膜成膜过程中热力学、流变学和凝胶动力学的影响

以酚酞基聚芳醚砜/草酸/N,N-二甲基乙酰胺为铸膜液体系, 考察了草酸对非对称膜成膜过程中的热力学、流变学和凝胶动力学的影响. 结果表明, 草酸的加入, 在热力学上加速了铸膜液的相分离. 成膜过程中凝胶动力学的研究结果表明, 凝胶前锋位移的平方与时间不是简单的线性关系. 将凝胶过程与非对称膜的结构相对应, 分为4个连续的凝胶过程, 凝胶速度曲线由4段具有不同速度常数的线段组成. 在凝胶过程中, 凝胶速度常数最大的是皮层.     

低温水凝胶力学性能的研究

本文采用单向压缩和单向拉伸法测定了聚乙烯醇(PVA)低温水凝胶的力学性能。结果表明,其机械强度随凝胶浓度和冷冻时间的增加而增强。得到弹性模量与凝胶浓度的关系符合标度律。说明采用低温处理方法可使PVA水溶液凝胶化,制得含水量高、具有较高强度、类似于橡胶的弹性材料,认为其力学强度来自于物理交联网络的贡献。     

磁场敏感性水凝胶研究进展

磁场敏感性水凝胶是一类由聚合物三维网络和磁性组分所构成的复合凝胶,其在药物控制释放、人工肌肉、酶的固定与蛋白质分离等领域具有良好的应用前景。本文综述了磁场敏感性水凝胶的制备方法及其在上述领域的应用。     

Nonlinear viscoelasticity, percolation and particles dispersibility of PVA/aluminum hydroxide composite gels

We investigated the rheological properties of a composite gel consisting of poly(vinyl alcohol) and aluminum hydroxide particles, and discussed the relation among nonlinear viscoelasticity, percolation and particles dispersibility. The dynamic viscoelastic measurements revealed that the storage modulus at volume fractions ? < 0.04 satisfied with the Krieger-Dougherty equation representing random dispersion of particles. The storage modulus did not show any nonlinear viscoelastic response at ? < 0.04. However, the storage modulus at ? > 0.06 took a value which is far larger than that expected by the equation, indicating heterogeneous distribution of particles. Additionally, the nonlinear viscoelastic response was recognized clearly at ? > 0.06, suggesting a partial contact between particles. The storage modulus at ? > 0.18 showed a further increase satisfied with the percolation theory, therefore, the volume fraction is considered to be the percolation threshold of 3-dimension. Microscopic observations of the gel showed a clear network with a mesh size of few μm that is considered to be a partial network of particles.     

Phase behavior actuating morphology and rheological response of polybutadiene/polyisoprene blends under small amplitude oscillatory shear

The morphology evolution and the corresponding linear viscoelastic behavior of the phase-separating polybutadiene （PB）/low vinyl content polyisoprene （LPI） blend have been investigated by phase contrast optical microscopy （PCOM）, small-angle light scattering （SALS） and rheometxy. Two kinds of structure evolutions and rheological responses have been observed. It is found that the co-continuous structure generally gives a power law behavior of the dynamic storage modulus versus frequency and the coarsening of co-continuous structure leads to a decrease of the storage modulus. For the droplet-matrix structure, a platform modulus is observed at the mediate frequencies, followed by the typical terminal relaxation behavior of storage modulus at the extremely low frequencies. The decreasing platform modulus and increasing terminal modulus with the growth of droplets are observed and can be well interpreted by the simplified Palieme model. The platform modulus and terminal modulus at a given frequency are found to be scalable with the phase separation time. Besides, the characteristic relaxation time and domain size of the droplets have been obtained by theology. And it seems that the theologically determined droplet dimensions are consistent with the ones determined by PCOM and SALS.     

烷基链长及肽链电荷分布对脂肽双亲分子自组装及水凝胶化的影响

为阐明脂肽分子烷基链长及肽链电荷分布对其自组装及水凝胶化的影响, 设计合成了C_nV₃K₂ (n=12, 14, 16) 和C_mKV₃K (m=14, 16)两个系列的脂肽分子. 原子力显微镜(AFM)和透射电镜(TEM)结果表明, 两个系列的脂肽分子都可以自组装成一维纳米带结构. 圆二色(CD)光谱结果表明, C_nV₃K₂系列自组装体的二级结构为β折叠; C_mKV₃K系列自组装体中包括α螺旋和β折叠两种二级结构, 其中C14KV3K的α螺旋结构较多, C16KV3K的β折叠结构占优. 烷基链疏水作用的增强会抑制β折叠结构侧向堆积, 使纳米带随烷基链的变长而变窄; 电荷分布于肽链部分的两端有利于纳米带结构的侧向生长. 流变性测试结果表明, 在浓度10 mmol·L^-1、pH 8.4下, 脂肽分子可以形成自支撑水凝胶, 相比烷基链长度, 肽链部分的电荷分布对水凝胶性能影响更大.     

Mechanical properties of polyamide-12 layered silicate nanocomposites and their relations with structure

The mechanical properties of polyamide-12/Cloisite 30B (PA12/C30B) nanocomposites prepared by melt compounding were studied as a function of clay volume fraction φ under various processing conditions. All measured mechanical characteristics, Young's modulus, yield stress, strain at break and stress at break, exhibit a transition at φ_p1%, identified with a percolation threshold. Also, the linear and non-linear mechanical properties appeared to depend on the degree of exfoliation of the structure, which can be tuned by the processing conditions. The three-phase Ji's theoretical model was used to predict Young's modulus as a function of clay concentration, focusing on the influence of the degree of exfoliation. Experimental yield stress data were fitted to Pukanszky's model and discussed in terms of PA12/C30B interfacial adhesion.     

Liposomal drugs dispersed in hydrogels. Effect of liposome, drug and gel properties on drug release kinetics

Release of calcein and griseofulvin (GRF) from control (gels in which solutes are dissolved in) and liposomal gels was studied using agarose-assisted immobilization as a technique to separate gels from drug-receptor compartments. Liposomes composed of phosphatidylcholine (PC) or distearoyl-glycero-PC and cholesterol (DSPC/Chol), and incorporating calcein or GRF were prepared by thin film hydration. After cleaning the liposomes they were dispersed in different hydrogels (carbopol 974 [1, 1.5 or 2% (w/w)], hydroxylethyl-cellulose (HEC) [4% (w/w)], or a mixture of the two), and release of calcein or GRF was followed by fluorescence or photometric technique, respectively. Results show that calcein release from liposomal gels is slower compared to control gels, and can be further retarded by using rigid-membrane liposomes (faster release from PC-liposome compared to DSPC/Chol-liposome gels). Additionally, calcein release is not affected by the lipid amount loaded (in the range from 2 to 8 mg/ml), therefore solute loading can be controlled according to needs.

Oppositely, GRF release from liposomal gels is determined by drug loading. At high drug loading levels (compared to GRF aqueous solubility), GRF is released with constant rate from liposomal gels irrespective of liposome type (PC or DSPC/Chol). Thereby, for amphiphilic/lipophilic drugs, drug properties (solubility, log P) determine the system behavior.

Calcein and GRF release from control carbopol gels is faster compared to HEC and mixture gels. The same is true for calcein in liposomal gels. Carbopol gel rheological properties were found to be significantly different (compared to the other gels), implying that these characteristics are important for drug diffusion from gels.     

Effects of pH on dynamics and rheology during association and gelation via the Ugi reaction of aqueous alginate

Effects of solution pH on the physical properties of a semidilute aqueous alginate solution without cross-linker agent and during gelation via the Ugi multicomponent condensation reaction at a fixed cross-linker concentration have been investigated. Both rheology and turbidity results on the alginate solution without cross-linker revealed enhanced associations at low pH. In the course of the cross-linker reaction, the time of gelation is shortest at pH = 3.5 and at pH values above 3.8 no gel is formed but only a viscosification of the solution is observed. The turbidity during the cross-linking reaction rises as the pH increases from 3.5 to 5. Furthermore, the initial change of the turbidity in the course of the cross-linking process is more pronounced at higher pH. The dynamic light scattering (DLS) results of the reaction mixture at pH = 4.0 (ergodic features at this condition) show that the chain relaxation is slowed down as the reaction proceeds. The effect of pH on the kinetics of the Ugi reaction is discussed.     

On hydrogen-bonded complexes: the case of (HF)2

The hydrogen fluoride dimer (HF)₂ is the most completely characterized hydrogen bonded species incorporating a donor molecule and an acceptor molecule. We provide a summary of experimental and theoretical information pertinent to the fundamental and harmonic vibrational frequencies, equilibrium geometry and dissociation energiesD _e andD ₀ as well as a brief critical discussion including some new results on the potential function and current best estimates of experimental quantities.