Thixotropy of Aqueous Suspensions Containing Mg‐Al Hydrotalcite‐like Compound and Low‐substituted Cationic Starch: Comparison between Oscillatory Shear and Thixotropic Loop Measurements

The rheological properties of aqueous suspensions consisting of positively charged aluminum magnesium hydrotalcite‐like compound (HTlc) and low‐substituted cationic starch (LCS) were investigated. Special emphasis was placed on the thixotropic phenomenon. Thixotropic behavior was investigated by two thixotropic methods: thixotropic loop and oscillatory shear measurements. LCS molecules could be adsorbed onto HTlc particles due to the hydrogen bonding between ether groups or hydroxyl groups of LCS and hydroxyl groups of HTlc. The elastic dynamic response of the HTlc/LCS suspension increased with increasing mass ratio (R) of HTlc and a three‐dimensional network structure could be formed in the suspension with higher R value. The thixotropic type of the HTlc/LCS suspension transformed from negative to positive and then to complex thixotropy when R changed from 0 to 0.5. By comparing between the thixotropic results obtained by thixotropic loop and oscillatory shear measurements, it was validated that the thixotropic loop for the suspension showing complex thixotropy had a crossover point.     

Rheological behavior of aqueous suspensions containing cationic starch and aluminum magnesium hydrotalcite-like compound in the presence of different electrolytes

The rheological properties of aqueous suspensions consisting of cationic starch (CS) and positively charged aluminum magnesium hydrotalcite-like compound (HTlc) in the presence of different electrolytes (NaCl, CaCl₂ and AlCl₃) were investigated. It is found that the network-like structure of pure CS solution is formed by the interaction between CS molecules. Both the equilibrium viscosities and the elastic response of CS solution decrease with the addition of NaCl, CaCl₂ and AlCl₃. Small amplitude sinusoidal oscillation tests show that a three-dimensional network of the HTlc/CS suspension can be formed through the bridge effect between CS molecules and HTlc particles due to the hydrogen bonding between the ether groups or hydroxyl groups of CS and the hydroxyl groups of HTlc. Both the equilibrium viscosity and dynamic property of the HTlc/CS suspensions indicate that the network-like structural strength of the suspensions increases firstly and then decreases with increasing HTlc content. The equilibrium viscosity and the elastic response of the HTlc/CS suspensions decrease gradually with the addition of NaCl or CaCl₂, but decrease firstly then increase and then decrease with increasing AlCl₃ concentration, i.e., the structural strength of the HTlc/CS suspensions can be strengthened by the addition of appropriate amount of AlCl₃ content.     

Thixotropic properties of aqueous suspensions containing cationic starch and aluminum magnesium hydrotalcite-like compound

The rheological properties of aqueous suspensions consisting of cationic starch (CS) and positively charged aluminum magnesium hydrotalcite-like compound (HTlc) were investigated. Special emphasis was placed on the thixotropic phenomena. With the increase of mass ratio (R) of HTlc to CS, the equilibrium viscosity (eta(eq)) and the consistency coefficient (m) values of the suspensions increase in the range of neutral and alkaline pH (higher than 6.5) while decrease in the range of acid pH (lower than 6.5). With the increase of pH value, the eta(eq) and m values of the suspensions in the R range of 0-0.08 studied increase initially and then decrease, appearing a maximum value at about pH 7.41+/-0.25. The CS/HTlc suspensions display viscid character and the yield point of the suspensions was not observed except the suspension with R=0.08 in the pH range of 7.66-9.70, which showed a yield point and viscoelasticity. The CS/HTlc suspensions may display different thixotropic types: negative, complex or positive thixotropy, depending on pH and R value. The thixotropic type of the CS/HTlc suspension may be transformed from negative (pure CS solution), through complex (R=0.02), into positive thixotropy (R=0.05 and 0.08) with the increase of R in the studied R range of 0-0.08, and the thixotropic strength of the suspensions increases initially and then decreases with pH value in the pH range studied. The mechanism of the thixotropic phenomenon is discussed.     

Influence of Mg2+ Contents on the Thixotropy of HTlc/MT Suspensions

In this article, we found that the variation of Mg²⁺ content in the Fe-Al-Mg hydrotalcite-like compounds (HTlc) and the change of R values (R_defined = W_HTlc /W_MT) will influence the thixotropic and viscoelastic properties of HTlc/sodium montmorillonite (MT) suspensions. With increasing the content of Mg²⁺ in the HTlc samples, the storage modulus (G′) and the loss modulus (G″) of the HTlc/MT suspensions will increase gradually, which means the structure strength of the HTlc/MT suspension increases with increasing of Mg²⁺ content in the HTlc samples. In addition, the structure strength of the suspensions will increase with increasing of R values. Special emphasis has been laid on the phenomenon of thixotropy. As the gradual increase of the structure strength in the HTlc/MT suspension, the thixotropic types will change accordingly. The mechanism has been discussed emphatically.     

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.     

Influence of Montmorillonite's Concentration on the Thixotropy of Hydrotalcite-like Compounds/Montmorillonite Suspensions

In this paper, we found that the change of sodium montmorillonite's (MT) concentration in the magnesium‐aluminum‐ferrum hydrotalcite‐like compounds (Mg‐Al‐Fe‐HTlc)/MT suspensions would greatly influence the thixotropic type of the suspensions. Specifically, the increase in the MT's concentration increases the viscosities (η) of the HTlc/MT suspensions with the same R value (the mass ratio of HTlc to MT was signed as R, e.g., R=m_HTlc/m_MT), meaning that the structure strength of the HTlc/MT suspensions increases. With the variation of MT's concentration, the thixotropic type of the HTlc/MT suspensions changed accordingly, and the mechanism has been discussed in this paper.     

无机电解质及聚合物对Mg-Al混合金属氢氧化物—高岭土分散体系触变性的影响

类水滑石;流变学;无机电解质及聚合物对Mg-Al混合金属氢氧化物—高岭土分散体系触变性的影响     

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。     

镁铝类水滑石对邻、间、对甲基苯酚的吸附

采用液相非稳态共沉淀法制备了镁铝类水滑石（Mg-Al HTlc）,并研究了邻、间和对甲基苯酚在Mg-Al HTlc上的吸附行为。 结果表明,邻、间和对甲基苯酚在Mg-Al HTlc上的吸附等温方程均符合Freundlich吸附等温式;吸附动力学均符合准二级动力学方程;在实验范围内,Mg-Al HTlc对三者的吸附量为：对甲基苯酚＞邻甲基苯酚＞间甲基苯酚;在pH值5.00~13.00范围内,三者的吸附量均随pH值的增加先增大后减小、随温度升高和电解质（NaCl）浓度的增大而增大。 探讨了吸附机理和苯环上甲基取代基位置对吸附的影响。     

类水滑石/蒙脱土体系的特殊粘弹性和触变性研究

本文对由类水滑石（HTlc） /钠质蒙脱土（MT）组成的复杂体系的粘弹性和触变性进行了详细的研究,我们共研究了两种Fe-Mg-Al- HTlc样品,从样品1到样品2,Al 对 Fe的比例保持不变,而Mg2+的含量逐渐增加。研究发现,随着类水滑石中Mg2+的含量增加,HTlc/MT分散体系的结构强度逐渐增加;触变环的实验结果也表明,随着类水滑石中Mg2+的含量增加,HTlc/MT分散体系的触变程度逐渐增加。由此我们可以得到这样的结论,通过调节类水滑石金属的配比我们就可以对类水滑石/蒙脱土体系的流变性进行宏观的调节。     

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(0～0.091)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.     

Study on the thixotropy of aluminum magnesium hydroxide– Na-montmorillonite suspension

 In this paper, the thixotropy of the aqueous suspension consisting of aluminum magnesium hydroxide (AMH) possessing permanent positive charges and Na-montmorillonite possessing permanent negative charges was studied. Besides positive thixotropy and negative thixotropy, a novel thixotropic phenomenon was found, i.e., a given system studied may display, early and late, positive M28.8nthixotropic character and negative thixotropic character, we describe it as “complex thixotropy”. The content of the suspension and electrolyte may influence the forms of thixotropy of the suspension studied. Received: 4 February 1997 Accepted: 15 October 1997     

类水滑石对低取代度阳离子淀粉的吸附行为

研究了低取代度阳离子淀粉（CS-L）在Mg-Al类水滑石（HTlc）上的吸附行为。 CS-L可在带结构正电荷的Mg-Al HTlc表面吸附,吸附方程符合Langmuir等温式,300 min左右达吸附平衡,饱和吸附量为33.92 mg/g。 吸附驱动力可能缘自于：CS-L醚键或羟基与HTlc羟基之间形成氢键;熵效应,即吸附所引起的CS的熵减少小于被吸附水释放引起的熵增加。 随着pH值的增加,CS-L和HTlc的Zeta电位均降低,二者静电排斥作用减小,吸附量增加;惰性电解质NaCl和CaCl2的加入可屏蔽HTlc与CS-L之间及CS-L分子内带正电的链段之间的静电排斥力,吸附量增加;pH=9时,带负电的Al八面体多聚体容易吸附在带结构正电荷的HTlc表面进而吸附CS分子,吸附量显著增加;温度升高降低二者氢键作用,吸附量降低。 比较了CS-L与高取代度阳离子淀粉（CS-H）在Mg-Al HTlc上的吸附行为。     

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。     

Effect of Electrolytes and Polymers on the Thixotropy of Mg‐Al‐Layered Double Hydroxides/Kaolinite Dispersions

The effect of electrolytes (NaCl and CaCl₂) and polymers (CPAM and HPAM) on the thixotropy of Mg‐Al‐layered double hydroxide (LDHs)/kaolinite dispersions has been investigated. It was observed that the type of thixotropy in LDH/kaolinite dispersions may be affected by NaCl, but not by CaCl₂ in range of concentration of interest. The type of thixotropy in LDH/kaolinite dispersion with R=0 transformed from positive thixotropy to complex thixotropy and at last positive thixotropy again with the concentration of NaCl in range of 0.00–0.10 mol·L⁻¹; the type of thixotropy in LDHs/kaolinite dispersions with R=0.25 transformed from complex thixotropy to positive thixotropy and then complex thixotropy again with the concentration of NaCl in range of 0.00–0.10 mol·L⁻¹. The type of thixotropy in LDH/kaolinite dispersion with R=0 may be not affected by cationic polyacrylamide (CPAM) and hydrolyzed polyacrylamide (HPAM); but the LDHs/kaolinite dispersions with R=0.25 transformed from complex thixotropy to positive thixotropy with the both polymers concentration in range of interest, which indicated that the microstructure of the dispersion changed from weak folc sediments structure to steric network structure.     

羧甲基纤维素钠/蒙脱土悬浮体系的流变性能及其影响因素

考察了蒙脱土(MT)质量分数(w)、羧甲基纤维素钠(CMC)/MT质量比(R)、电解质(NaCl、MgCl2和AlCl3)、pH值和温度对MT或CMC/MT悬浮体系流变性能和触变性的影响。 结果表明,随w增加,纯MT悬浮体系的流体类型由近牛顿流体向塑型流体变化,触变类型则由无触变、正触变向复合触变性转变;而CMC/MT悬浮体系仍保持MT体系的正触变塑型流体特征,但屈服值τ0和稠度指数K增加,滞后环面积S和电动电势|ζ|先增加后减小,表现出同步变化。 电解质和实验温度均不改变CMC/MT悬浮体系的正触变性塑型流体特征,但电解质使τ0和K增加,而温度增加使τ0和K减小。 随介质pH值的增加,CMC/MT体系由负触变性变为正触变性,|ζ|增大,S先增加后减小,且在pH=8.46时达到最大。     

Influence of pH on the thixotropy of magnesium aluminum hydroxide-kaolinite suspension

The influence of pH on the thixotropy of pure kaolinite suspension and magnesium aluminum hydroxide (Mg-AI-MMH)-kaolinite suspension was studied. The results show that the thixotropic type of pure kaolinite suspension was not affected by pH studied in the range of 3.60-12.00. The thixotropic type of Mg-AI-MMH-kaolinite suspension with mass ratio (R) value of MMH to kaolinite 0.029 transformed from complex thixotropy into positive thixotropy with increasing of pH in the range of pH 3.83-12.00, and the type of thixotropy of Mg-AI-MMH-kaolinite suspension with R = 0.129 transformed from positive thixotropy into complex thixotropy with increasing of pH in the range of pH 3.70-11.96.     

盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白,用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDSPAGE)确定为Ⅰ型胶原;红外及紫外光谱表明胶原分子中存在三螺旋结构.分别采用小幅振荡剪切法、恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响.研究表明,随盐酸胍浓度的增大及作用时间的延长,盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体.在所研究的盐酸胍浓度范围(0~6.0 mol/L)内,盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变;随盐酸胍作用时间的延长(6~48 h),盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变.本文的研究结果有助于加深对触变性产生机理的认识.     

盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白, 用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)确定为Ⅰ型胶原; 红外及紫外光谱表明胶原分子中存在三螺旋结构. 分别采用小幅振荡剪切法、 恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响. 研究表明, 随盐酸胍浓度的增大及作用时间的延长, 盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体. 在所研究的盐酸胍浓度范围(0~6.0 mol/L)内, 盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变; 随盐酸胍作用时间的延长(6~48 h), 盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变. 本文的研究结果有助于加深对触变性产生机理的认识.     

Zn-Al类水滑石的荧光性质

报道了一种新的Zn-Al类水滑石的荧光现象, 即在没有任何荧光物质插层的情况下, Zn-Al类水滑石本身就具有荧光性质, 其最大激发波长位于375 nm, 最大发射波长处于443 nm, 显示的荧光为蓝色可见光. 这一光学功能的发现将有助于类水滑石在光学材料领域中的进一步应用.