Rheology and UV protection properties of suspensions of fine titanium dioxides in a silicone oil

Ultrafine particles of titanium dioxide (TiO2) are very attractive as a UV protection ingredient in cosmetic products. The UV-scattering behavior of TiO2 suspensions in a silicone oil are studied in relation to rheological properties. To control the dispersion stability of suspensions, two types of polyether-modified silicones are used as dispersants. When the suspensions are prepared with branch-type dispersants in which the polyether groups are incorporated as side chains along the backbone, the flow is shear-thinning even at low shear rates. The appearance of plateaus in the frequency-dependence curves of storage modulus implies the solidlike responses. On the other hand, the suspensions prepared with linear conformation dispersants, in which the silicone group and polyether group are alternately repeated in one long chain, are Newtonian at low shear rates. The suspensions are regarded as liquids, because the storage modulus decreases rapidly in the low-frequency region. The suspension rheology is strongly associated with flocculated structures that are primarily controlled by the interparticle attractions. The differences in rheological behavior can be explained by the differences in the adsorbed conformation of dispersant silicones. From optical measurements, it is confirmed that UV scattering increases with decreasing flocculation degree. Therefore, good agreement is established between rheological properties and UV protection ability.     

Effect of associating polymer on the viscosity behavior of suspensions consisting of particles with different surface properties

Associating polymers which consist of water-soluble long-chain molecules containing a small fraction of hydrophobic groups (hydrophobes) behave as flocculants in aqueous suspensions. The effects of associating polymers on the rheological behavior are studied for single suspensions of particles with hydrophilic and hydrophobic surfaces, and their mixtures. For particles with hydrophilic surfaces, the suspensions are highly flocculated by a bridging mechanism, because the water-soluble chains adsorb onto hydrophilic surfaces. On the other hand, the particles with hydrophobic surfaces cannot be dispersed in water without polymer and the additions of a small amount of polymer are required for preparation of homogeneous suspensions. The associating polymer acts as a dispersant at low concentrations. However, further additions of polymer lead to a drastic increase in viscosity. Since the hydrophobes on one end of molecules adsorb onto hydrophobic surfaces and other hydrophobes tending from the particles can form micelles, the particles are connected by linkage of interchain associations. By mixing two suspensions of particles with hydrophilic and hydrophobic surfaces, the viscosity is substantially reduced and the flow becomes nearly Newtonian. The associating polymer in complex suspensions acts as a binder between the hydrophilic and hydrophobic surfaces. The hetero-flocculation which leads to the formation of composite particles may be responsible for the viscosity reduction of complex suspensions.     

Colloidal stabilization of nanoparticles in concentrated suspensions

The stabilization of nanoparticles in concentrated aqueous suspensions is required in many manufacturing technologies and industrial products. Nanoparticles are commonly stabilized through the adsorption of a dispersant layer around the particle surface. The formation of a dispersant layer (adlayer) of appropriate thickness is crucial for the stabilization of suspensions containing high nanoparticle concentrations. Thick adlayers result in an excessive excluded volume around the particles, whereas thin adlayers lead to particle agglomeration. Both effects reduce the maximum concentration of nanoparticles in the suspension. However, conventional dispersants do not allow for a systematic control of the adlayer thickness on the particle surface. In this study, we synthesized dispersants with a molecular architecture that enables better control over the particle adlayer thickness. By tailoring the chemistry and length of these novel dispersants, we were able to prepare fluid suspensions (viscosity < 1 Pa.s at 100 s-1) with more than 40 vol % of 65-nm alumina particles in water, as opposed to the 30 vol % achieved with a state-of-the-art dispersing agent. This remarkably high concentration facilitates the fabrication of a wide range of products and intermediates in materials technology, cosmetics, pharmacy, and in all other areas where concentrated nanoparticle suspensions are required. On the basis of the proposed molecular architecture, one can also envisage other similar molecules that could be successfully applied for the functionalization of surfaces for biosensing, chromatography, medical imaging, drug delivery, and aqueous lubrication, among others.     

Shear-thickening flow of nanoparticle suspensions flocculated by polymer bridging

The steady-shear viscosity, dynamic viscoelasticity, and stress relaxation behavior were measured for suspensions of silica nanoparticles dispersed in aqueous solutions of poly(ethylene oxide) (PEO). The suspensions of silica with diameters of 8-25 nm show striking shear-thickening profiles in steady shear and highly elastic responses under large strains in oscillatory shear. Since the silica particles are much smaller than the polymer coils, one molecule can extend through several particles by intrachain bridging. Each polymer coil may remain isolated as a floc unit and the silica particles hardly connect two flocs. Therefore, the flow of suspensions is Newtonian with low viscosity at low shear rates. When the polymer coils containing several nanoparticles are subjected to high shear fields, three-dimensional network is developed over the system. The shear-thickening flow may arise from the elastic forces of extended bridges. But, the polymer chain is easily detached from particle surface by thermal energy because of large curvature of particles. As a result, the network structures are reversibly broken down in a quiescent state and the suspensions behaves as viscoelastic fluids with the zero-shear viscosity.     

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。     

Preparation of stable aqueous suspensions of antimony-doped tin oxide nanoparticles used for transparent and thermal insulation fluorocarbon coating

In order to prepare the highly stable aqueous suspensions of antimony-doped tin oxide (ATO) used for the transparent and thermal insulation fluorocarbon coating, the effect of sodium polyacrylate (PAAS) and polyvinyl alcohol (PVA) on the stability of the suspensions was investigated. The stability and dispersity of the suspensions were characterized using zeta potential analyzer, ultraviolet–visible spectrophotometer, and scanning electron microscope. No sediments were observed after 6-month storage of the ATO suspensions containing 0.1 wt% PAAS and 2.0 wt% PVA. The reason why aqueous suspensions were capable of stabilization was explained from a theoretical perspective. A new model of steric hindrance for colloid particles stabilized by binary dispersant was proposed, which may have positive contribution to other colloid system containing two dispersants. A nano-composite fluorocarbon coating, exhibiting a good thermal insulation and high transmittance, was formed after ATO suspensions were added in fluorocarbon emulsion. The temperature inside the chamber was decreased by 6.0 °C, and 75.0 % visible light rays could pass through the coating.     

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.     

Size effect on the rheological behavior of nanoparticle suspensions in associating polymer solutions

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups and tend to create bonds between chains by reversible associating interactions. The effects of associating polymer on the steady-shear viscosity and dynamic viscoelasticity are studied for suspensions of silica nanoparticles with diameters of 8, 18, and 25 nm. The silica particles of 8 nm are entrapped in the transient network of associating polymer by reversible adsorption. The enhancement of network results in the high viscosity with a Newtonian flow profile in the limit of zero shear rate. In suspensions of 25 nm silica, the hydrophobes extending from the chains adsorbed onto different particles can form a micelle by association interactions. The multichain bridging gave rise to the shear-thinning flow and high storage modulus at low frequencies. The suspensions of 25 nm silica are characterized as flocculated systems. Because of intermediate curvature, the flexible bridges are formed between silica particles of 18 nm. When the flexible bridges are highly extended within the lifetime in shear fields, the suspensions show shear-thickening flow. The shear-thickening flow can be attributed to the elastic effect of flexible bridges.     

Rheological properties of filled polymers

The rheological properties of two model suspensions using a Newtonian polymeric matrix are presented and discussed in light of results presented in the literature. It is shown that particle-particle interactions in concentrated suspensions are responsible for a gel-type behavior at very small strain and strain hardening at a critical strain. Suspensions of concentrated colloidal particles in a Newtonian matrix behave like typical viscoelastic molten polymers, but the properties are strongly dependent on the solids dispersion, and strain at small strain. A simple rheological model is proposed to describe the shear viscosity of these suspensions.     

催化剂浆液制备条件对Pt/C催化剂电化学性能的影响

研究了催化剂浆液分散时间和分散剂等制备条件对Pt/C催化剂电化学活性的影响.结果表明,催化剂浆液的超声振荡时间和分散剂对Pt/C催化剂性能影响很大.当超声分散10 min时,对应的电化学性能最好;低于10 min时,催化剂的分散不够完全,性能较差;超声分散时间过长,则由于浆液温度升高使得样品颗粒团聚长大,导致Pt/C电...     

Dispersant adsorption and viscoelasticity of alumina suspensions measured by quartz crystal microbalance with dissipation monitoring and in situ dynamic rheology

Adsorption behavior and water content of adsorbed layers of four dispersants for aqueous ceramic processing were studied by quartz crystal microbalance with dissipation monitoring (QCM-D) on alumina surfaces. The dispersants were a poly(acrylic acid), a lignosulfonate, and two hydrophilic comb copolymers with nonionic polyoxyethylene chains of different molecular weights. A Voigt model was applied to analyze the viscoelastic behavior of the adsorbed dispersant layers. The results from QCM-D were compared with viscoelastic properties determined by in situ dynamic rheology measurements of highly concentrated alumina suspensions during slip casting. The QCM-D results showed that both the poly(acrylic acid) and the lignosulfonate adsorbed in low amounts and in a flat conformation, which generated thin, highly rigid layers less than 1 nm thick. The water content of these layers was found to be around 30% for the lignosulfonate and 35% for the poly(acrylic acid). High casting rate and strength in terms of storage modulus were observed in the final consolidate of the suspensions with the two polyelectrolytes. In contrast, the high molecular weight comb copolymer adsorbed in a less elastic layer with a thickness of about 6 nm, which is enough to provide steric stabilization. The viscous behavior of this layer was attributed to high water content, which was calculated to be around 90%. Such a water-rich layer gives a lubrication effect, which allows for reorientation of particles during the consolidation process, resulting in a high final strength of the ceramic material. During consolidation, the suspension showed a slow casting rate, most likely due to rearrangement facilitated by the lubricating layer. The short-chain comb copolymer adsorbed in a 1.5 nm thick, rigid layer and gave low final strength to the consolidated suspension. It is likely that the poor consolidation behavior is caused by flocculation due to insufficient stabilization of the dispersion.     

Flow‐induced particle orientation and rheological properties of suspensions of organoclays in thermoplastic resins

The influence of nano‐scale particles on the viscoelastic properties of polymer suspensions is investigated. We have developed a simulation technique for the particle orientation and polymer conformation tensors to study various features of the suspensions. The nano‐particles are modeled as thin rigid oblate spheroid particles and the polymers as FENE‐P type viscoelastic and Newtonian fluid. Both interparticle and polymer‐particle interactions have been taken into account in our numerical computations. The nonlinear viscoelastic properties of nanocomposites of layered silicate particles in non‐Newtonian fluids are examined at the start‐up of shear flow and are interpreted using the model to examine the effects of model parameters as well as flow conditions on particle orientation, viscosity, and first normal stress difference of the suspensions. We have studied the microstructure of polymer‐clay nanocomposites using X‐ray diffraction (XRD) scattering and transmission electron microscopy (TEM). The rheology of these nanocomposites in step‐shear is shown to be fairly well predicted by the model. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2003–2011, 2010     

Rheological Characterization of Alumina Ceramic Suspensions in Presence of a Dispersant and a Binder

The rheological responses of aqueous alumina suspensions, stabilized with an organic polyvalent salt dispersant called “Aluminon,” and including a poly(vinyl) alcohol (PVA) binder, are described in this study. It is observed that the addition of PVA, without any dispersant does not significantly influence the rheology. However, in the presence of the dispersant the rheology is affected significantly. At a given concentration of the dispersant, the viscosity, the storage and loss modulii all increase with the PVA concentration. Also, for a given concentration of the PVA, the viscosity, the storage and loss modulii values increases as the concentration of the dispersant is increased. At relatively low PVA concentrations, an excess concentration of the dispersant, causes flocculation of the particles in the suspension by a reduction of the electrostatic (double layer) effect. On the contrary, at higher concentrations of the PVA the flocculation of the suspension occurs via a depletion mechanism.     

Viscosity behavior of silica suspensions flocculated by associating polymers

Associating polymers are hydrophilic long-chain molecules containing a small number of hydrophobic groups, and act as flocculants in aqueous suspensions. The effects of associating and nonassociating polymers on viscosity behavior are studied for silica suspensions. Since flocculation is induced by polymer bridging, the viscosity behavior is converted from Newtonian to shear-thinning profiles. The additions of surfactant cause an increase in viscosity for suspensions prepared with associating polymer, whereas the flow behavior of suspensions with nonassociating polymer is not significantly influenced. In adsorption of associating polymers onto silica particles, the chain may adopt a conformation with a water-soluble backbone attached to the particle surfaces. The hydrophobic groups extending from the chains adsorbed onto different particles can form a micelle by association with surfactant. Therefore, the bridging flocculation is enhanced by surfactant. The cooperative micellar formation between associating polymer and surfactant is responsible for viscosity increase in suspensions.     

Stress jumps on weakly flocculated dispersions: steady state and transient results

Weakly flocculated, thixotropic suspensions have been investigated by means of fast stress jump experiments. With a suitable procedure, reliable stress relaxation data could be collected starting 20 ms after cessation of flow. This technique has been used to determine the elastic and hydrodynamic contributions to the shear stress. Steady state as well as transient flows have been studied for suspensions containing either fumed silica or carbon black particles in a Newtonian medium. In both systems, the elastic stress totally dominates the response at low shear rates and consequently also the apparent yield stress. This stress contribution becomes negligibly small at high shear rates. The hydrodynamic contribution to the viscosity has finite limits at both the low and high shear rate ends. The data are relevant for testing rheological models. As an illustration, it is shown that the data agree qualitatively with the model proposed by Potanin et al. (J. Chem. Phys. 102 (14) (1995) 5845-5853).     

Dispersion Characterization of Short Slag Fiber in Aqueous Solution

Slag fiber with desirable properties is a promising candidate for applications as fillers or reinforced materials. Its poor dispersion in bulk materials, however, becomes the major challenge. Some aspects of its physicochemical properties were focused upon in the present article. The effect of three kinds of dispersants, viz., sodium carboxymethyl cellulose (CMC), anionic polyacrylamide (APAM), and cationic polyacrylamide (CPAM), as well as their combinations on the dispersion of slag fiber in aqueous solution was investigated. The viscosities of fiber suspensions were measured and the results were correlated with the dispersion of suspensions. It was shown that the slag fiber appeared amorphous, smooth surface with high length/diameter (L/d) ratio and negatively charged in water. The dispersion of slag fiber in aqueous solution directly depended on the dispersants. The optimal uniform and stable fiber suspension could be achieved under the dispersant concentration of the combination of 2 wt% CMC and 0.25 wt% APAM. In this case, the fiber concentration was as large as 25 g/L. In addition, the plausible dispersion mechanism of slag fiber in aqueous solutions was elucidated based on the electrostatic steric stabilization.     

Flow-induced ordering of particles and flow velocity profile transition in a tube flow of graphene oxide dispersions

We measured the S- and P-order parameters of flow-induced ordered graphene oxide (GO) particles and the flow velocity profiles for a flowing aqueous GO dispersion in a tube, by using an optical method. The order parameters clearly exhibit increasing concentric biaxial ordering as the flow velocity increases, with the exception of a disordered centre. Newtonian to non-Newtonian transition in the flow velocity profile is found, changing from a parabolic shape to a fuller shape at very low Reynolds numbers less than 10. This is attributed to the shear thinning effect (i.e., an ordering-induced reduction in viscosity). In the Newtonian flow, a uniaxial ordering was dominant; whereas a biaxial ordering sharply increased in the non-Newtonian flow, indicating that both the ordering of GO particles and the interparticle interactions influence the flow profile transition.     

A novel method for preparing and characterizing alcoholic EPD suspensions

Ceramic suspensions composed of alumina and mixtures of alumina and zirconia powders in ethyl alcohol were prepared. A solution of citric acid and triethylamine was used as dispersant. The citric acid, which usually is used as dispersant in water alumina suspensions, gave excellent results in ethyl alcohol also if it was used in conjunction with triethylamine. A novel method consisting of combined measurements of grain size, zeta potential, and transmittance was optimized to study the dispersion and stability properties of the ceramic suspensions; by using this method the optimal dispersant amount was determined. The suspensions based on alumina and alumina-zirconia powders were used to coat stainless steel plates by electrophoretic deposition (EPD); the optimal composition of suspensions and the used EPD parameters made it possible to obtain coatings with uniform thickness and composition.     

分散剂对水焦浆成浆性影响的量子化学研究

为高效利用半焦资源,选择适宜的水焦浆分散剂以提高兰炭制备水焦浆的性能,本研究以陕北半焦及四种不同分散剂(腐植酸钠SH、木质素磺酸钠SLS、十二烷基磺酸钠SDS和一种自制衣康酸型分散剂IPMS)为研究对象,探讨了不同添加剂对水焦浆成浆特性的影响。利用Material Studio(MS)软件计算了分散剂的结构参数及半焦与分散剂间的相互作用能,从量子化学角度对分散剂的作用进行探讨,并与制浆实验结果进行比较。结果表明,加入分散剂可有效降低液体表面张力,增大半焦颗粒表面电负性,从而增强颗粒间静电排斥作用使得浆体更加稳定。相同制备条件下,分散剂IPMS制备水焦浆时效果较优,在剪切速率为100 s~(-1)时,其表观黏度为625 mP·s,7 d析水率仅为2.38%且无硬沉淀。通过计算机模拟得出吸附过程中分散剂的氧原子向半焦的羟基一侧靠近,产生电荷转移,四种分散剂活性大小顺序为IMPS SH SLS SDS,IMPS与半焦相互作用的吸附作用较强与实验结果一致。证明了采用量子化学计算结合实验数据可以对水焦浆分散剂的性能进行评价,为浆体燃料制备技术及新型药剂的设计开发提供了理论基础。     

Effect of Polyvinylpyrrolidone on Rheology of Aqueous SiC Suspensions Stabilized with Polyacrylic Acid

The effect of polyvinylpyrrolidone (PVP) on rheology of aqueous SiC suspensions stabilized with polyacrylic acid (PAA) was investigated. At pH 6.0, as the total amount of dispersants was fixed at 0.3 wt%, the suspensions with co-addition of PAA and PVP obtained much lower viscosity than those added separately, displaying Newtonian behavior. The improvement in rheology of SiC suspensions arose from enhanced steric hindrance, which was caused by the presence of PVP molecules in association with PAA molecules adsorbed on SiC particle surfaces. However, this effect was relatively weak in alkaline condition because of complete dissociation of PAA.