Mg-Fe-HTlc/高岭土悬浮体流变性研究

研究了Mg-Fe类水滑石(HTlc)/高岭土(kaolinite)悬浮体的质量比(R)对其流变性和触变性的影响, 发现控制剪切速率(D)得到的屈服应力(τy)和控制剪切应力(τ)得到的临界剪切应力(τc)皆随R的增大先降低后升高. 小幅振荡剪切实验发现随R 的增大, 体系由正触变性转化为复合触变性, 其中用小幅振荡剪切法在线性粘弹区发现复合触变性体系还是首次. 恒剪切速率(DL)实验发现了震荡现象, 即粘度随时间发生周期性升高和降低的变化. 震荡现象与DL 和R 有关,较高的DL 和R 可使震荡现象消失. 测定粘度随时间变化时采用的低剪切速率(DL)影响体系的触变性类型. 根据HTlc和kaolinite 粒子间的相互作用对实验结果的机理进行了探讨.     

Al-Mg MMH正电胶体粒子体系的流变学

研究了铝／镁混合金属氢氧化物（MMH）粒子含量,PH值,电解质等因素对MMH悬浮液流变学的影响,发现MMH粒子浓度的增加使悬浮体从牛顿型流体变为带有屈服值的假塑性流体;在相对很低的粒子浓度（2％）时,通过改变粒子表面化学状态和粒子周围的介质环境可以改变悬浮体的流动形态;MMH悬浮体触变性结构与高PH值时合成锂皂石悬浮体的结构极为相似,是粒子间的静电排斥作用所致。     

Mg-Fe-HTIc／高岭土悬浮体流变性研究

研究了Mg—Fe类水滑石(HTIc)／高岭土(kaolinite)悬浮体的质量比（R)对其流变性和触变性的影响，发现控制剪切速率(D)得到的屈服应力(τy)和控制剪切应力(τ)得到的临界剪切应力(τc)皆随R拘增大先降低后升高．小幅振荡剪切实验发现随R的增大，体系由正触变性转化为复合触变性，其中用小幅振荡剪切法在线性粘弹区发现复合触变性体系还是首次．恒剪切速率(DL)实验发现了震荡现象，即粘度随时间发生周期性升高和降低的变化．震荡现象与DL和R有关，较高的DL和尺可使震荡现象消失．测定粘度随时间变化时采用的低剪切速率(DL)影响体系的触变性类型．根据HTIc和kaolinite粒子间的相互作用对实验结果的机理进行了探讨．     

Fe-Al-Mg-MMH/钠质蒙脱土分散体系触变性研究

研究了 Fe-Al-Mg型混合金属氢氧化物 (简称 MMH) /钠质蒙脱土 (简称 MT)分散体系的触变性 ,发现在不同 MMH/MT质量比 ( R)条件下 ,分散体系可分别呈现正触变性和负触变性 .在所研究的 R范围( 0～ 0 .0 91 )内 ,随 R增大 ,体系的触变性发生正触变性 -复合触变性 -负触变性的转化 .考察了高速剪切分散后 ,测定粘度变化前的静置时间 ( ts)和测定粘度时的剪切速率 ( DL)对触变性的影响 .探讨了各种触变性产生的原因 ,提出了“分散粒子 -空间连续网络结构 -密实聚集体”和“分散粒子 -密实聚集体 -密实聚集体簇”机理 ,较合理地解释了观察到的复合触变现象     

Fe—AI—Mg—MMH／钠质蒙脱土分散体系触变性研究

研究了Fe-AI-Mg型混合金属氢氧化物（简称MMH）／钠质蒙脱土（简称MT）分散体系的触变性,发现在不同MMH／MT质量比（R）条件下,分散体系可呈现正触变性和负触变性。在所研究的R范围（0－0．91）内, 随R增大,体系的触变性发生正触变性－复合触变性－负触变性的转化。考察了高速剪切分散后,测定粘度变化前的列置时间（ts)和测定粘度时的剪切速率（DL)对触变性的影响。探讨了各种触变性产生的原因,提出了“分散粒子－空间连续网络结构－密实聚集体”和“分散粒子－密实聚集体－密产聚集体簇”机理,较合理地解释了观察到的复合触变现象。     

二氧化硅悬浮体和水解聚丙烯酰胺体系的流变性

研究了二氧化硅悬浮体的流变性。在固体含量较少的情况下, 体系呈Newton型;固体含量达到一定程度以后, 产生三维结构, 为假塑性体系。三维结构的固体含量与pH值有关。实验证实, 在等电点(i,e, p)附近三维结构最为疏松。还研究了水解聚丙烯酰胺(HPAM)对悬浮体流变性能的影响。HPAM破坏了二氧化硅粒子聚集体结构, 呈絮凝体结构, 并出现触变性。当高聚物在固体表面覆盖一半时, 具有最大触变性和动剪切力。HPAM的水解度达到一定程度, 由于对固体粒子由“强”吸附转变为“弱”吸附, 固体粒子“屏蔽”了高分子间的相互作用, 出现了负触变性现象。在流动时粒子会脱附, 静止以后又产生吸附, 这种吸附与脱附是产生负触变性的主要原因。HPAM水解过度或用量过多, 均会减弱负触变性现象。     

剪切速率对Fe-Al-Mg-MMH/钠质蒙脱土悬浮体触变性的影响

研究了测定条件对Fe-Al-Mg型混合金属氢氧化物（简称MMH）/钠质蒙脱土（简 称MT）混合悬浮体及纯MT体系触变性的影响，主要考察了高速剪切分散后，剪切速 率（D_L）对粘度（η）～时间（t）变化趋势的影响。发现纯的MT体系和MMH/MT质 量比（R）为0.013的Fe-Al-Mg-MMH/MT体系在所研究的D_L下（10，170，511和1 022 s~(-1)）都呈现为正触变性，D_L不影响触变性类型。R = 0.051的体系，低 D_L时（10和170 s~(-1)）呈现复合触变性，高D_L时（511和1 022 s~(-1)）呈现 正触变性；R = 0.091的体系在低D_L时（10和170 s~(-1)）呈现负触变性，在高 D_L时（511和1 022 s~(-1)）呈现复合触变性。D_L增加，各体系η逐渐降低。对 D_L影响触变性的机理进行了深入探讨。     

剪切速率对Fe-Al-Mg-MMH/钠质蒙脱土悬浮体触变性的影响

研究了测定条件对Fe-Al-Mg型混合金属氢氧化物（简称MMH）/钠质蒙脱土（简 称MT）混合悬浮体及纯MT体系触变性的影响，主要考察了高速剪切分散后，剪切速 率（D_L）对粘度（η）～时间（t）变化趋势的影响。发现纯的MT体系和MMH/MT质 量比（R）为0.013的Fe-Al-Mg-MMH/MT体系在所研究的D_L下（10，170，511和1 022 s~(-1)）都呈现为正触变性，D_L不影响触变性类型。R = 0.051的体系，低 D_L时（10和170 s~(-1)）呈现复合触变性，高D_L时（511和1 022 s~(-1)）呈现 正触变性；R = 0.091的体系在低D_L时（10和170 s~(-1)）呈现负触变性，在高 D_L时（511和1 022 s~(-1)）呈现复合触变性。D_L增加，各体系η逐渐降低。对 D_L影响触变性的机理进行了深入探讨。     

Mg-Fe-MMH-钠质蒙脱土分散体系的触变性研究

触变性是分散体系一种复杂的流变学性质,指流变性质随剪切时间而发生变化的现象。以往研究过程中,先后发现了切稀现象和切稠现象,即正触变性和负触变性。最近,我们又发现了复合触变性,即一个体系可先后呈现正触变性和负触变性特征。研究了Mg-Fe型混合金属氢氧化物(简称MMH)-钠质蒙脱土(简称MT)分散体系的触变性,发现在不同MMH/MT质量比条件下,可分别呈现正触变性、负触变性,另外双观察到了复合触变性。在所研究的MMH/MT质量比范围(0～0.5)内,随MMH/MT质量比增大,体系的触变性发生负触变性-正触变性-复合触变性-负触变性的转化。考察了电解质NaCl对触变性的影响,发现不改变触变性的类型。探讨了各种触变性产生的原因,提出了“分散粒子-空间连续网络结构-密实聚集体”机理,较合理地解释了观察到的复合触变现象。     

带相反电荷胶体颗粒混和悬浮体的流变学性能

研究了带相反电荷的粘土颗粒和MMH(铝、镁混合金属氢氧化物)颗粒形成的混和悬浮体的流变学性能,考察了盐对混合体系流变学性能的影响.结果表明,当粘土质量分数为1%时,悬浮体为牛顿型流体;当质量分数升至2%时,悬浮体表现出固体的弹性响应;特定粘土含量的悬浮体中,随着MMH量的增加,混合体系的屈服值和弹性模量亦增加,表明凝胶结构增强.向混合体系中加入NaCl,弹性模量、屈服值和粘度等流变参数均降低.与单组分粘土悬浮体或MMH悬浮体相比,双组分混合体系的结构恢复很快.     

Influence of Electrolytes on the Thixotropy of Ferric Aluminum Magnesium Hydroxide‐Montmorillonite Suspensions

Abstract

The thixotropy of suspensions consisting of ferric aluminum magnesium hydroxide (Fe‐Al‐Mg‐MMH) and Na‐montmorillonite (MT) is examined with special emphasis on the influence of electrolytes. When NaCl or MgCl₂ is added into the Fe‐Al‐Mg‐MMH/MT suspension, the thixotropy of the suspension may change (if positive) from positive and complex into negative, but NaCl or MgCl₂ can't alter the thixotropic type of a negatively thixotropic suspension. When AlCl₃ was added to positive thixotropic system can be transformed to a complex one, whereas a complex and negative thixotropic suspension remains unchanged, for additions less than 0.01 mol/L; when the addition level of AlCl₃ increases, all types of thixotropic systems are changed to non‐thixotropic. In addition, NaCl and MgCl₂ make the initial viscosity measured after cessation of intensive shearing increase, but the value of the viscosity decreased rapidly with time. The equilibrium viscosity of the suspension decreased gradually with increasing concentrations of NaCl and MgCl₂ in the suspension. With increasing concentration of AlCl₃, the equilibrium viscosities of the positive thixotropic suspension and the complex thixotropic suspension increase at first, but decrease later, and the equilibrium viscosity of negative thixotropic suspensions decrease gradually.     

Rheology of silica-filled polystyrene: From microcomposites to nanocomposites

Rheology and viscoelastic behavior of polystyrene (PS)/silica microcomposites and nanocomposites were studied. The apparent viscosity, transient shear stress growth after startup shear flow and stress relaxation after cessation of flow at various shear rates, the complex dynamic viscosity, the storage and loss moduli at small and large strain amplitudes and various frequencies were performed. The effect of size, shape and volume concentration of silica was discussed. The maximum volume concentration, corresponding to the concentration at which the relative viscosity of mixtures goes to infinity, with respect to the hydrodynamic contribution of the particles and to polymer-filler interactions was obtained. The difference between the yield stress and residual stress is shown. The domain of equivalence between the apparent viscosity as a function of the shear rate in steady state flow and the complex dynamic viscosity as a function of the strain rate amplitude in highly nonlinear region of oscillatory flow was established. The viscoelastic behavior was interpreted based on the morphology of microcomposites and nanocomposites observed by SEM.     

Mesoscale constitutive modeling of magnetic dispersions: material functions for shear flows

We recently developed a constitutive model for magnetic dispersions by modeling the magnetic particles as rigid dumbbells dispersed in a solvent. The theory yielded a constitutive equation in which the stress tensor could be expressed as a function of the velocity gradient, an orientational order tensor, S, an average alignment vector, J, and any imposed external magnetic field, H. The constitutive equation is used here to predict material functions for steady shear flow (shear-rate dependent viscosity and first normal stress coefficient) as well as those for unsteady shear flows (stress growth upon inception of steady shear and small-amplitude oscillatory shear). The importance of effects of concentration, equilibrium nematic ordering in the dispersion, and anisotropy in the hydrodynamic drag are emphasized. Comparisons with available experimental data on viscosity for magnetic inks under steady shear flow and inception of steady shear flow show reasonably good agreement.     

STRUCTURING & RHEOLOGY OF MOLTEN POLYMER/CLAY NANOCOMPOSITES

The evolution and the origin of "solid-like state" in molten polymer/clay nanocomposites are studied. Using polypropylene/clay hybrid (PPCH) with sufficient maleic anhydride modified PP (PP-MA) as compatibilizer, well exfoliation yet solid-like state was achieved after annealing in molten state. Comprehensive linear viscoelasticity and non-linear rheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time,temperature and deformation dependencies of the "solid-like" state in molten nanocomposites. Based on these, it is revealed that the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA,the diffusion and association of exfoliated silicate platelets, the formation of band/chain structure and, finally, a percolated clay associated network, which is responsible for the melt rigidity or solid-like state. The network will be broken down by melt frozen/crystallization and weakened at large shear or strong flow and, even more surprisingly, may be disrupted by using trace amount of silane coupling agent which may block the edge interaction of platelets. The solid-like structure causes characteristic non-linear rheological behaviors, e.g. residual stress after step shear, abnormal huge stress overshoots in step flows and, most remarkably, the negative first normal stress functions in steady shear or step flows. The rheological and structural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chains connecting clay particles or by chains in confined melts or frictional interaction among tactoids. A scheme of percolated networking of associated clay platelets, which may in band form of edge connecting exfoliated platelets, is suggested to explain previous experimental results.     

Mg-Al-MMH-高岭土分散体系触变性研究

触变性是分散体系流变学研究的重要内容之一,在外切力作用下,若体系的粘度随时间下降,静止后又恢复,即具有时间因素的切稀现象,称为正触变性（positive thixotropy);反之,若体系的粘度或切力上升,静止后又恢复,即具有时间因素的切稠现象,称之为负触变性（Negative thixotropy)^[1],若在外切力作用下,某个特定体系的粘度或切力随时间先后呈现出正触变性和负触变性特征,则称之为复合触变性（Complex thixotropy)^[2,3],目前,对各种触变性机理的认识尚不统一。     

STRUCTURING ＆ RHEOLOGY OF MOLTEN POLYMER／CLAY NANOCOMPOSITES

The evolution and the origin of “solid-like state” in molten polymer/clay nanocomposites are studied. Using polypropylene/clay hybrid (PPCH) with sufficient maleic anhydride modified PP (PP-MA) as compatibilizer, well exfoliation yet solid-like state was achieved after annealing in molten state. Comprehensive linear viscoelasticity and non-linear rheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time,temperature and deformation dependencies of the “solid-like” state in molten nanocomposites. Based on these, it is revealed that the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA,the diffusion and association of exfoliated silicate platelets, the formation of band/chain structure and, finally, a percolated clay associated network, which is responsible for the melt rigidity or solid-like state. The network will be broken down by melt frozen/crystallization and weakened at large shear or strong flow and, even more surprisingly, may be disrupted by using trace amount of silane coupling agent which may block the edge interaction of platelets. The solid-like structure causes characteristic non-linear rheological behaviors, e.g. residual stress after step shear, abnormal huge stress overshoots in step flows and, most remarkably, the negative first normal stress functions in steady shear or step flows. The rheological and structural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chains connecting clay particles or by chains in confined melts or frictional interaction among tactoids. A scheme of percolated networking of associated clay platelets, which may in band form of edge connecting exfoliated platelets, is suggested to explain previous experimental results.     

Preparation and rheological characterization of poly(n-butyl methacrylate)/montmorillonite composites

Intercalated nanocomposites constituted of poly(butyl methacrylate) (PBMA) as the matrix and an organically modified montmorillonite as the nanosize filler were prepared and rheologically characterized in detail. The rheological behavior of the composites showed dependence on both temperature and clay content. For composites of low clay contents, the steady shear viscosity showed a Newtonian plateau in the low shear rate region at low temperatures and the plateau was replaced by a shear-thinning curve when the temperature was raised. For composites of higher clay contents, strong shear-thinning behavior were observed at all shear rates and all temperatures. The viscoelastic data of the composites showed unusual terminal behavior of a decreasing terminal slope at low frequencies with increasing temperature and clay loading. X-ray diffraction spectra showed that annealing process at higher temperatures shifted the Bragg reflection peaks to a lower angle and broadened the peaks, which provided the evidence for the existence of a temperature-induced solid-like structure that was responsible for the shear thinning and the unusual terminal viscoelastic behavior.