Effect of Surface-Active Substances on the Rheological Properties of Silicon Carbide Suspensions in Paraffin

In this paper, the possibility of stabilization of SiC suspensions in paraffin (hot-molding slips) was investigated from the colloid science point of view. By considering the surface properties of finely dispersed silicon carbide, surface-active agents (fatty amine and alkylsuccinimide) which are suitable for surface modification by chemical adsorption on SiC were selected. Adsorption of fatty amines and alkylsuccinimide was carried out in model experiments in chloroform. Increasing the length of the carbon–hydrogen chain caused the adsorption to decrease, and the adsorption area of one molecule in the saturated adsorption layer to increase. The stabilizing effect of surface-active agents resulted in improved flow behavior of hot-molding slips. The efficiency of surface-active agents increased with increased adsorption layer thickness. In highly concentrated SiC hot-molding slips, a combination of alkylsuccinimide and fatty amine proved to be very efficient. This synergistic effect of long- and short-chained surface-active agents is discussed in terms of an adsorption layer model.     

Effects of Ammonium Chloride on the Rheological Properties and Sedimentation Behavior of Aqueous Silica Suspensions

The influence of ammonium chloride (NH₄Cl) on the rheological properties and sedimentation behavior of aqueous silica (SiO₂) suspensions of varying solids volume fraction (φ_s) was studied. SiO₂ suspensions with low NH₄Cl concentration (≤0.05 M , pH 5.2) exhibited Newtonian behavior and a constant settling velocity ( U ). The volume fraction dependence was well described by the Richardson–Zaki form, U = U ₀(1 −φ_s) ⁿ , where n = 4.63 and U ₀= 1.0419 × 10⁻⁵ cm/s. At higher NH₄Cl concentrations (0.07–2.0 M , pH 5.2), suspensions exhibited shear thinning and more complicated sedimentation behavior due to their aggregated nature. For all suspensions studied, however, the apparent suspension viscosity, characteristic cluster size, and initial settling velocity were greatest at ∼0.5 M NH₄Cl and exhibited a similar dependence on salt concentration. Above 0.5 M NH₄Cl, considerable restabilization was observed. This behavior cannot be explained by traditional DLVO theory.     

Electrokinetic and Rheological Properties of Aqueous TiN Suspensions with Ammonium Salt of Poly(methacrylic acid)

The study illustrates how rheology and electrokinetics can be utilized in the investigation and optimization of the properties of ceramic suspensions. Zeta potential studies show that the isoelectric point of TiN particulates is at pH=4, and for the pH range used, PMAA–NH₄ addition results in a more negative zeta potential value. The rheological behavior of titanium nitride in the presence of PMAA–NH₄ is strongly dependent on pH and three rheological types have been defined.     

Drying Suspensions in a Pulsed Fluidized Bed of Inert Particles

The drying of carbohydrate suspensions on polypropylene particles in a pulsed fluidized bed was studied by means of a 2⁵ experimental design, to determine the effect of the air flow and temperature, suspension flow rate, and free section and rotating speed of the rotary plate on the Nusselt number, the moisture content of the product, and the percentage of solids retained inside the bed (which were minimized to 4.9 and 14.4%, respectively) with an air flow of 600 m³/h at 90°C and 720 mmHg, a suspension flow rate of 6 L/h, and a plate with 6% free section, rotating at 50 rpm.

Additionally, the effects of temperature, air flow, and suspension flow rate on the residence time distribution (RTD) were determined, using the stimulus-response methodology. The RTD was represented by 1.1 to 2 tanks in series, according to this model. The mean residence time of the dried carbohydrate particles was between 5.4 and 8.2 min.

Finally, an egg suspension could be dried at 4 L/h, with air at 90°C, with a mean residence time about 50% longer that that found for drying carbohydrate suspensions.     

Drying Suspensions in a Pulsed Fluidized Bed of Inert Particles

The drying of carbohydrate suspensions on polypropylene particles in a pulsed fluidized bed was studied by means of a 2⁵ experimental design, to determine the effect of the air flow and temperature, suspension flow rate, and free section and rotating speed of the rotary plate on the Nusselt number, the moisture content of the product, and the percentage of solids retained inside the bed (which were minimized to 4.9 and 14.4%, respectively) with an air flow of 600 m³/h at 90°C and 720 mmHg, a suspension flow rate of 6 L/h, and a plate with 6% free section, rotating at 50 rpm.

Additionally, the effects of temperature, air flow, and suspension flow rate on the residence time distribution (RTD) were determined, using the stimulus-response methodology. The RTD was represented by 1.1 to 2 tanks in series, according to this model. The mean residence time of the dried carbohydrate particles was between 5.4 and 8.2 min.

Finally, an egg suspension could be dried at 4 L/h, with air at 90°C, with a mean residence time about 50% longer that that found for drying carbohydrate suspensions.     

In Situ Rheological Investigation of the Coagulation in Aqueous Alumina Suspensions

Electrostatically stabilized alumina suspensions can be destabilized by the enzyme-catalyzed decomposition of urea (direct coagulation casting). Depending on the conditions, this reaction can shift the pH of a suspension to the buffer pH of the reaction products or increase the ionic strength at the buffer pH. The coagulation for both mechanisms was investigated using in situ rheological measurements. Using a vane tool in oscillation mode, the measuring conditions were optimized to find a reasonable method for time-dependent measurements. Constant parameters (stress or strain) proved to be unsuitable, because the linear viscoelastic region shifted considerably during the coagulation. Furthermore, the gel structure produced on coagulation via increase of ionic strength (Δ I ) was very sensitive to the oscillation. Therefore, for long-time experiments, a short continuous measurement with a low strain was followed by amplitude sweeps with increased intervals to determine the linear values of G ' and G ". In this way, the increase of the moduli G ' and G " could be followed for longer times, and it was possible to demonstrate two results. First, the final G ' of the network was about 10 times higher for Δ I -coagulated material than for suspensions coagulated via pH shift (ΔpH). Second, particle rearrangement processes took place in Δ I -coagulated networks even after the chemical changes were finished, whereas ΔpH-coagulated samples were "frozen-in" when approaching the isoelectric point and showed no further physical changes afterward.     

微嵌段缔合聚合物溶液的线性粘弹性

通过高级流变仪测试了不同微嵌段长度的缔合聚合物溶液的剪切稀释特性和线性粘弹性。测试结果表明,在临界缔合浓度之上,其幂律指数和松弛时间在NH=30.8时出现极值,证实缔合聚合物的非牛顿特性和线性粘弹性并不是随嵌段长度增加而单调增加的,这与一般缔合聚合物的规律不一致;在临界缔合浓度以下,其非牛顿特性和线性粘弹性随着嵌段长度增加而逐步增加。因此嵌段长度通过影响缔合效应的强度进而影响缔合聚合物的粘弹性。     

Time-Dependent Adhesion-Induced Phenomena: Viscoelastic Creep of a Substrate Polymer Over Rigid Particles

The adhesion of micrometer-size particles to an alternating block copolymer composed of polydimethyisiloxane and polyester was found to be accompanied by substantial viscoelastic flow of the substrate polymer. This flow gave rise to contact radii, which were substantially larger than those predicted by the JKR theory. Moreover, tensile-induced creep of the substrate resulted in anomalously large menisci that actually flowed up several particle heights. The flow of the material occurred over a period of days and, in some instances, the observed contact radii were greater than a critical radius for substantial engulfment of the particles by the substrate. Craters were left behind after particle removal, suggesting plastic-rather than elastic response of the substrate polymer to the surface-force-induced stresses. Size-exclusion chromatography has identified the presence of lower molecular weight polydimethylsiloxane-rich copolymer species in the n-hexane soluble mobile phase responsible for the unexpected behavior exhibited by this polymer substrate.     

Effect of 2-Phosphonobutane-1,2,4-tricarboxylic Acid Adsorption on the Stability and Rheological Properties of Aqueous Nanosized 3-mol%-Yttria-Stabilized Tetragonal-Zirconia Polycrystal Suspensions

2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) was evaluated as a dispersant for nanosized 3-mol%-Y₂O₃-stabilized tetragonal-ZrO₂ polycrystal (3Y-TZP) suspensions. The adsorption of PBTCA was characterized using the decolorization method of ferric 5-nitrosalicylate complexes. Maximum adsorption of the dispersant on the 3Y-TZP powder was found to occur at pH 3.0. At pH >3.0, the adsorbed amount decreased with increased pH. Semiquantitative analysis using auger electron spectroscopy showed that PBTCA adsorbed irreversibly on the powder. The surface charge of the powder was evaluated by measuring the zeta-potential in dilute powder suspensions. The suspension was most effectively stabilized at high pH by the high charge induced by the adsorption of PBTCA. Rheological properties of the suspension were evaluated as a function of dispersant amount and solids loading. The optimum amount of dispersant increased with increased solids loading for solids loading >20 vol%. A stable suspension of 35 nm 3Y-TZP particles with a solids loading as high as 32 vol% was obtained using PBTCA as dispersant, in contrast to 28 vol% when using ammonium polyacrylate (NH₄PAA). Theoretical calculations of the interaction between 3Y-TZP particles showed that the stabilization of the suspensions was attributed to a combination of the electrostatic repulsion and a steric barrier caused by the adsorbed PBTCA. Induced coupling plasma analysis showed that PBTCA could be completely burned out during sintering, which confirmed its suitability as a dispersant for 3Y-TZP.     

In Situ Surface Modification of Silicon Carbide Particles Using Al3+ Complexes and Polyelectrolytes in Aqueous Suspensions

Silicon carbide (SiC) particles were modified in situ , using Al³⁺ complexes in aqueous media, via control of Al(NO₃)₃concentration and pH. The Al³⁺ formed hydrolyzed complexes that adsorbed onto the charged sites on the SiC particle surfaces. As a result, the surface-modified SiC particles behaved in an alumina-like manner in the approximate pH range 5–8. The modified SiC particles were further treated with two types of polyelectrolytes that were sequentially adsorbed onto the particle surface, to give a maximum surface charge. As a result of this surface-modification process, the SiC could be dispersed with Al₂O₃in aqueous media without heteroaggregation.     

Influence of Acidity on the Stability and Rheological Properties of Ionically Stabilized Alumina Suspensions in Ethanol

The ionic stability of alumina particles in moderately concentrated ethanol suspensions is studied. Surface chemistry and interparticle forces are manipulated by controlling the acidity of the suspensions without dispersants. The acidity of ethanol solution is determined using ion transfer functions, wherein the relationships between acidity, alumina particle surface charge, zeta-potential, stability, and suspension rheological behavior are established. Positive isoelectric point (IEP) shift is observed for alumina in ethanol on increasing the solids concentration. However, dilute and concentrated aqueous suspensions of alumina give the same IEP. The viscosity and flow curves for alumina/ethanol suspensions are acidity dependent. The flow curves of the suspensions follow the Casson model, and the Casson yield value is used to evaluate suspension stability.     

Properties of a semi-crystalline and an amorphous thermotropic liquid crystalline polymer

The physical properties, thermal stability, rheology and tensile properties of a commercial semi-crystalline and an amorphous thermotropic liquid crystalline polymer (TLCP) have been investigated. Analysis by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) confirm the presence of a small melting endotherm and a glass transition in the former material. The as-received amorphous TLCP exhibits no obvious melting endotherm and a strong glass transition is detected. The flow and tensile properties of the semicrystalline polymer are dominated by the presence of the crystalline to nematic transition temperature. The properties of the amorphous TLCP appear to be governed by increasing mobility afforded by increasing temperature. Based on flow behaviour and further DSC analysis it has been shown that under appropriate annealing conditions the as-received amorphous TLCP can develop solid crystalline order.     

Linear Viscoelastic Characteristics of Poly(trimethylene terephthalate)/Polycarbonate Blends in the Melt State

Summary: Blends of poly(trimethylene terephthalate) (PTT) and polycarbonate (PC) over full composition range were prepared using a twin‐screw extruder. A glycidyl methacrylate‐based terpolymer was used to modify the interface of the blends. Morphological examinations were carried out using transmission electron microscopy (TEM) and confirmed the biphasic structure of the blends. Dynamic rheological response of the blends was recorded in the linear viscoelastic region. It was observed that addition of the terpolymer to the system increases the dynamic shear moduli and complex viscosity of the blends, which is attributed to interactions of the terpolymer at the interface of two phases leading to a restricted chain mobility of the blend components. The Veenstra model was found to be able to describe dynamic shear modulus of the PTT/PC 50/50 blend; however, for the compatibilized blend of PTT/PC 50/50, the fit is not as good as that of uncompatibilized system, which is believed to be due to formation of micelles in this system.

Dynamic storage modulus of the compatibilized and uncompatibilized PTT/PC blends.     

Storage modulus of polybutadiene core in acrylonitrile–butadiene–styrene polymers with different degrees of grafting

The linear viscoelastic behavior of acrylonitrile‐butadiene‐styrene (ABS) polymers in the molten state, with different degrees of grafting, was investigated within the framework of Palierne's emulsion model. The main aim of the present study is to quantitatively analyze the effect of grafting degree on the storage modulus G′ of the polybutadiene (PB) rubber core dispersed in ABS polymers. According to our model calculations, the degree of grafting significantly affects the G′ values of the PB core and, hence, the viscoelastic properties of ABS polymers. Our calculations showed that the Palierne model is very useful to calculate the storage modulus of the rubber particles dispersed in rubber‐modified polymeric materials, at least in the high‐frequency region. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 924–930, 2001     

Rheology of cubic particles in a concentrated colloidal dispersion suspending medium

The flow behavior of mixtures of micron‐sized cubic particles suspended in a concentrated colloidal dispersion is investigated across a broad range of cubic particle concentrations. In the semi‐dilute regime, the qualitative shape of the dynamic moduli and flow curves reflect those of the underlying colloidal dispersion medium. These curves are superimposed with the underlying colloidal dispersion using shift factors that are found to be larger than those obtained in a recent study of suspensions of non‐colloidal spherical particles in the same colloidal dispersion medium. At higher concentrations of cubic particles, deviations from this shifting procedure are apparent. Scaling calculations suggest depletion interactions are responsible for the increase in the low shear viscosity and confinement of the underlying colloidal dispersion can be expected to enhance the shear thickening behavior at high shear stresses. The results of this study provide guidance for formulating suspensions through control of particle shape and mixture concentration. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1091–1101, 2017     

团聚硼颗粒在HTPB富燃料推进剂中的流变特性

为了探索球形团聚硼颗粒的制备效果,对端羟基聚丁二烯(HTPB)黏合剂、不同类型的团聚硼颗粒与HTPB黏合剂以一定质量配比形成的悬浮液,以及含团聚硼颗粒HTPB富燃料推进剂流变特性进行了对比研究。结果表明,HTPB黏合剂的表观黏度随温度的升高而降低,最终趋于某一定值;在一定温度下,无定形硼粉经团聚改性后,团聚硼颗粒与HTPB形成悬浮液的表观黏度和屈服值较团聚前降低,且两者均随时间的增加而增加;采用含团聚硼颗粒的富燃料推进剂药浆的流变特性大大改善,有利于含硼富燃料推进剂能量的提高和燃烧性能的改善。     

Comparative rheological characteristics of industrial polyflavonoid tannin extracts

Commercial, industrially produced mimosa, quebracho, pine, and pecan polyflavonoid tannin extracts water solutions of different concentrations were examined by rheometry by measuring dynamic moduli both as a function of strain amplitude and at varying frequency. The water solutions of these materials have been found to behave in general mainly as viscous liquids at the concentrations that are generally used for their main industrial applications. Clear indications of viscoelastic response are also noticeable, among these the crossover of the elastic and viscous moduli curves at the lower concentrations of the range investigated, with some differences being noticeable between each tannin and the others—pine and quebracho tannin extracts showing the more marked viscoelastic behavior. Other than pH dependence (and related structural considerations), the parameters found to be of interest as regards the noticeable viscoelastic behavior of the tannin extracts were the existence in the solutions of labile microstructures that can be broken by applied shear. This is supported by the well‐known thixotropic behavior of concentrated, commercial polyflavonoid tannin extracts water solutions. Such microstructures appear to be due (1) to the known colloidal interactions of these materials already reported, or (b) to other types of secondary interactions between tannin oligomers and particularly between tannin and carbohydrate oligomers. The latter is supported by the dependence of this effect from both the average molecular masses of the tannin and of the carbohydrate oligomers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1634–1642, 2001     

Experimental investigation of the rheological behaviors of polypropylene in a capillary flow

The rheological characterization of polymer melts is strongly related to their material properties. In this study, we focused on the rheological behaviors of a polypropylene (PP) melt through a capillary die. With an advanced twin‐bore capillary rheometer with dies measuring 1.0, 0.5, and 0.25 mm in diameter, experiments were performed over a shear‐rate range of 3 × 10² to 5 × 10³ s^?1 at three temperatures, 210, 220, and 230 °C. The results demonstrate that the geometry dependence of the PP viscosity relied on the die diameter and the temperature of the PP melt. The viscosity values of the PP melt in the 0.25‐mm diameter die were higher than were those in the 0.5‐ and 1.0‐mm dies at 220 and 230 °C. However, the viscosity values in all of the tested dies were similar at 210 °C. The tendency for the viscosity to decrease as the temperature of the polymer melt increased weakened in the 0.25‐mm diameter die. As a result, the pressure applied to the PP melt in the 0.25‐mm diameter die increased; this caused a decrease in the free volume between molecules. On the basis of the Barus equation, the contribution of pressure to the changed viscosity in each die at each of the tested temperatures was calculated and was found to be as high as 32.86% in the 0.25‐mm die at 230 °C. Additionally, the effect of the wall slip on the geometry dependence of the PP viscosity in the tested dies was investigated with a modified Mooney method. The values of the slip velocity revealed that wall slip occurred only in the 0.25‐mm die at 210 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43459.     

Drying of Suspensions in a Fluidized Bed of Inert Particles Under Reduced Pressure

A drying method in which a heat-sensitive material is immersed in a fluidized bed under reduced pressure was used to continuously obtain dispersed, dry, fine powders of that material from a dilute suspension or solution at a low temperature with a high drying rate. The mass velocities of the drying gas, sample flow rate, and chamber pressure were varied, and the effects of these variations on the corresponding drying characteristics were examined.

The fluidization state of a fluidized bed of inert particles strongly affects the drying rate in the bed and has a greater effect than the chamber pressure on the corresponding drying characteristics. In other words, it is important to maintain a vigorous fluidization state to achieve a high drying rate. Although the maximum drying rate is independent of the chamber pressure, it can be achieved at a low mass velocity of the drying gas under reduced pressure. That is, at a low chamber pressure a high drying rate can be achieved, even at a relatively low mass velocity of the drying gas. The bed temperature at the time of drying is strongly influenced by the drying rate and decreases linearly with an increase in the maximum drying rate when the sample flow rate is equal to the drying rate.