Influence of pH and Ionic Impurities on the Adsorption of Poly(acrylic) Dispersant onto a Zinc Oxide Surface

We have studied the properties of aqueous suspensions of ZnO powders with different purities. Our results suggest that powder purity determines the amount of dispersant necessary to form a stable aqueous suspension as well as the maximum adsorption capacity of the dispersant: the higher the positive surface charge of the as-received ZnO powders, the higher the amount of dispersant adsorbed onto the metal oxide surface. The surface charge of the ZnO particles in suspension is affected by the concentration of zinc as well as sulfate ions, which are the major impurities in the supernatant. The pH of the aqueous ZnO suspensions increases with increasing concentration of poly(acrylic) dispersant until the maximum adsorption capacity is attained. Further additions of dispersant do not increase the pH because of a buffer formation with impurity ions.     

8%Y2O3-ZrO2水基料浆的流变性质研究

详细研究了固含量、球磨时间、分散剂用量和pH值对8％摩尔分数Y2O3稳定ZrO2水基料浆流变性质的影响。结果表明：料浆均表现出剪切变稀行为，且为假塑性流体。确定了最佳实验参数，当pH=10，分散剂用量为2％体积分数，球磨24h的ZrO2水基料浆，稳定性好，适合于成型薄片ZrO2固体电解质材料，并最终制备出体积分数为56％，适合浇注的ZrO2陶瓷料浆。     

分散剂用量对碳化硅浆料流变性能的影响

使用四甲基氢氧化铵(TMAH)作为分散剂,研究了分散剂用量对SiC浆料流变性能的影响,并分析了其原因。结果表明：TMAH能够显著提高SiC粉体的zeta电位,降低浆料粘度,从而显著优化浆料的流变性能。在pH为10左右,加入质量分数为0．3％和o．6％NTMAH后zeta电位分别提高了11.7mV和21mV。实验中,在不同体积分数SiC浆料中,加入0．6%TMAH时能够达到最优性能,浆料粘度都达到最低。过量的分散剂则会增加浆料中的离子浓度而导致双电层厚度减小,从而恶化浆料的流变性。     

Influence of Solid Fraction on the Optimum Molecular Weight of Polymer Dispersants in Aqueous TiO2 Nanoparticle Suspensions

The effects of solid fraction and molecular weight of a polymer dispersant—sodium polyacrylate—on the apparent viscosity of an aqueous TiO₂ nanoparticle suspension were investigated by varying the particle solid fractions from 15 to 37 vol% and the molecular weight of the dispersant from 1200 to 30 000. When the solid fraction was increased, the molecular weight of the dispersant was decreased to obtain the lowest suspension viscosity. The effect of the molecular weight of the dispersant on the suspension viscosity was discussed based on the surface interaction between TiO₂ particles characterized by a colloid probe atomic force microscope. The polymer dispersant adsorbed on a particle surface enhanced the repulsive force between the TiO₂ particles and reduced adhesion by electrosteric interaction, which reduced the suspension viscosity. The size of the dispersant in the aqueous solution determined by a dynamic light scattering method was compared with the estimated particle surface distance. As the solid fraction increased, the average surface distance and the size of the dispersant attainable to the particle surface reduced; therefore, the optimum molecular weight of the dispersant for a dense suspension is also reduced.     

Effects of dispersant concentration and pH on properties of lead zirconate titanate aqueous suspension

Lead zirconate titanate (PZT) aqueous suspensions were prepared at 60 wt.% solids loading using a commercial ammonium polyacrylate (APA) dispersant. Effects of the dispersant concentration on rheological behavior, dispersion and stability of PZT aqueous suspensions were investigated by means of zeta potential, viscosity and sedimentation height measurements. The results showed that, under suitable conditions, APA dispersant promoted particle dispersion and stabilization in PZT aqueous suspensions. For 60 wt.% solids loading suspensions, the dispersant concentration yielding the lowest viscosity was 0.5 wt.% based on PZT powder dried weight basis. Effects of pH on particle dispersion in the suspensions prepared with APA were studied by laser light scattering technique and scanning electron microscopy. The results showed an improvement in particle dispersion for the alkaline condition, which led to relatively low viscosity and highly stable suspension. Possible particle stabilization mechanisms at various pHs were discussed based on dissociation of the dispersant in water, polymer conformation and adsorption behavior of the dispersant on the particle surface.     

Production of a Highly Concentrated CaCO3 Suspension by Cross‐Flow Microfiltration in the Presence of a Dispersant

Abstract

This article presents the study of the cross‐flow microfiltration of an aqueous calcium carbonate suspension in the presence of dispersant in order to obtain the highly concentrated retentate. In the absence of a dispersant, the cross‐flow microfiltration with cylindrical ceramic membrane permitted to increase the CaCO₃ suspension concentration from 27 to 36.5%. The retentate concentration is increased markedly in the presence of the dispersant (up to 70%). In the presence of the dispersant, the productivity of cross‐flow microfiltration of CaCO₃ suspension is almost 30% higher than the productivity of dead‐end microfiltration of this suspension at the same pressure of 1 bar. However, the permeate contamination by the dispersant could not be avoided and a subsequent separation must be provided to purify the permeate.     

固体碳源在水溶液中的分散实验研究

在SiC陶瓷固相烧结过程中,碳源的分散性非常重要。其对陶瓷的微观组织结构和力学性能有较大的影响。本文重点通过沉降实验,研究对于同一分散介质,三种分散剂（无分散剂;Darven．C;焦磷酸钠）作用下,三种碳源（石油焦、炭黑、石墨）的不同分散结果,优选出分散最好的碳源以及分散性最佳的分散剂。实验结果表明：分散剂的加入对SiC浆料分散效果有很大影响;不同的碳源pH值有微小差别;三种碳源中碳黑分散最好;分散剂中焦磷酸钠分散性最佳。     

Rheology of Hydroxyapatite Dispersions

Hydroxyapatite (HA) is an interesting ceramic material for orthopedic applications, in particular for implant operations and bone regeneration, owing to its bioactivity and biocompatibility with the surrounding tissues. Even if different shaping processes can be used in order to obtain porous ceramic bodies with optimal final properties, the sponge impregnation method with aqueous HA dispersions is particularly suitable to achieve an appropriate macroporosity to bone regeneration. As for conventional slip or tape casting, the rheological behavior of HA suspensions must be properly fitted to process conditions and controlled through a satisfactory stabilization of the disperse phase, i.e., through an appropriate dispersant dosage and an accurate homogenization of dispersed powder. In the present work, HA powders with different crystallinity degree were used to prepare aqueous dispersions with different contents of solids and dispersant (ammonium polyacrylate). The specific surface area of HA powders is very high, and then special attention must be dedicated to the dispersant selection and the dispersion process since the rheology of HA suspensions is strongly influenced by the structural conditions of the disperse phase. Even small differences in dispersant concentration can lead to dramatic changes in the rheological properties also at relatively low values of solids volume concentration. Above a critical concentration, the viscosity drop associated with the apparently plastic behavior is confined within a very narrow stress range, a neat transition is observed in the linear viscoelastic properties, and the time-dependent effects induced by the shear history become quite important and crucial for the experimental characterization.     

High Thermal Conductivity Aluminum Nitride Substrates Prepared by Aqueous Tape Casting

High thermal conductivity aluminum nitride (AlN) substrates were prepared by aqueous tape casting. The characteristics of surface-treated AlN powder were studied in aqueous ball-milling media. The oxygen content of AlN powder with the dispersant was lower than that of AlN powder without the dispersant at the same ball-milling time. The isoelectric points of the surface-treated AlN with and without a dispersant were, respectively, at pH∼3.35 and pH∼3.90. The atmosphere had considerable effects on organic additive burnout of aqueous AlN green sheets. The composition of grain boundaries changed with increasing holding time at 1850°C. A translucent AlN substrate with a uniform microstructure and a thermal conductivity of 263 W·(m·K)⁻¹ was obtained by pressureless sintering at 1850°C for 6 h in a nitrogen atmosphere.     

Influence of dispersant structure and mixing speed on concrete slump retention

The relationship between rate of dispersant depletion from the aqueous phase and concrete slump retention was investigated by varying polycarboxylate dispersant structure and mixing speed. The influence of dispersant structure on the rate of slump loss was determined by testing two polycarboxylate-polyether dispersants that differed in charge density. The influence of mixing rate on slump loss was determined by changing mixer rotation speed. The rate of dispersant depletion was influenced by dispersant structure and mixing speed. A higher rate of dispersant depletion was observed at higher mixing speed and with a polymer of higher charge density. In comparing the different mixing procedures, a good correlation was found between slump value and the number of drum revolutions, while a poor correlation was found between slump value and time. Concrete slump retention was influenced by the rate of dispersant depletion and the rate of dispersant depletion was influenced by dispersant structure and mixing speed.     

Aqueous Processing of Titanium Carbide Green Sheets

TiC sheets were prepared by an aqueous tape-casting process. The zeta potential measurement showed that the isoelectric point for TiC powders in the absence of dispersant had a pH value of ∼3.3. According to the surface properties of TiC powders, a cationic polymer PEI was selected as dispersant. In the presence of dispersant, the isoelectric point increased to a pH value of ∼10.4. The slip stability was determined by visual observation of the fluidity of the slip as well as the settling of the powders. Results showed that the amount of dispersant required to achieve a minimum of viscosity for 50 vol% suspensions was equal to 1.2 wt%. In the absence and presence of dispersant, stable slips could be obtained in the pH ranges 7–9 and 11–12, respectively. The rheological measurements showed that with PEI as dispersant, TiC suspensions exhibited a small time dependent behavior. With polyvinyl alcohol as binder and glycerol as plasticizer, suspensions showed a thixotropic feature. As-cast tapes were dried in air at room temperature. The results showed that it was possible to fabricate homogeneous green tapes with smooth surfaces from these suspensions.     

影响氧化铝水基料浆流变学特性的关键因素

用流变学的方法在RV-20型流变仪上研究不同条件,如:固含量、分散剂加入量、烧结助剂、增塑剂等对碱性氧化铝悬浮体的流变性的影响.结果表明:氧化铝陶瓷碱性料浆(pH＞7)在低的剪切速率(＜100 s-1)时,表现为剪切变稀.在水基料浆中添加MgO时,会发生强烈的水合反应,导致料浆失去流动性.增塑剂甘油的加入导致料浆粘度升高的幅度是有限的,不会对料浆固含量和浇铸工艺造成显著不利的影响.加入水溶性丙烯酸乳液后,在低的剪切速率下,料浆仍然呈现剪切变稀行为,随着乳液含量的增加,料浆的静态粘度逐渐增大.分散剂聚丙烯酸氨的加入量对料浆的稳定性具有显著的影响.在分散剂的加入量为固相质量的0.8%左右时,分散剂在陶瓷颗粒表面形成饱和吸附,此时料浆的稳定性达到了最佳状态.     

Effect of Concentration of Ammonium Poly(acrylate) Dispersant and MgO on Coagulation Characteristics of Aqueous Alumina Direct Coagulation Casting Slurries

Coagulation of aqueous alumina slurries prepared using various concentrations (0.43–1.04 wt% based on alumina) of ammonium poly(acrylate) dispersant by MgO has been studied for direct coagulation casting (DCC) of alumina. The slurries prepared at dispersant concentration below 0.84 wt% are not suitable for DCC at room temperature (∼30 ° C) as they undergo premature coagulation. Mixing the slurry with MgO at a low temperature of nearly 5 ° C slows down the reactions leading to coagulation and keeps the slurry viscosity low for a sufficient period of time. Coagulation of slurries prepared at a dispersant concentration of 0.92 wt% and above at room temperature requires MgO concentrations much higher than the equivalent amount required for reaction with the dispersant. This anomalous behavior at higher dispersant concentration is explained such that the Mg-poly(acrylate) formed by the reaction between ammonium poly(acrylate) and MgO formed a sheath over the remaining MgO particles and prevented them from further dissolution at room temperature. Faster coagulation could be achieved by heating the slurries after casting in closed molds. The Mg-poly(acrylate) acts as a binder and stabilizes the coagulated bodies as their strength and stability against oscillatory stresses increase with an increase in dispersant concentration.     

Preparation of aluminum nitride green sheets by aqueous tape casting

Aluminum nitride green sheets were prepared by aqueous tape casting. The characteristics of a treated AlN were studied in aqueous ball-milling media. The oxygen content picked up with the increase of ball-milling time. It was noted that the oxygen content of AlN powder with the dispersant DP270 was lower than that of AlN powder without the dispersant DP270. The isoelectric points of the treated AlN with and without DP270 were, respectively, at pH 3.35 and pH 3.90. The dispersant DP270 not only efficiently dispersed AlN powder in water to form a stable suspension, but also formed a coat onto AlN surface to limit hydrolysis of the AlN powder. The tape casting slurry exhibited a typical shear-thinning behavior. Aqueous AlN green tape had a smooth surface and a narrow pore size distribution. Its relative density was 52.6%. No other crystalline phase was detected by XRD except for AlN and sintering aid yttria in AlN green sheet.     

Tape casting of PLZST tapes via aqueous slurries

A well-dispersed aqueous slurry for tape casting of PLZST (Pb_0.97La_0.02Zr_0.66Sn_0.23Ti_0.11) was prepared. Properties of PLZST slurries with and without polyelectrolyte dispersant were characterized by zeta potential, sedimentation etc. The experimental results show that the pH value of the slurries is changing with ball-milling time, and that the polyelectrolyte dispersant has a significant effect on the isoelectric point of PLZST. TGA analysis indicates that the organic additives in the green tapes can be completely removed by heat treatment at 600 °C. The density of PLZST ceramics is tightly related to the plasticizer and the sintering temperature. However, the results demonstrated that it is possible to prepare a dense PLZST thick film through aqueous slurry tape casting.     

Photopolymerization synthesis of polyacrylic acid dispersant with methoxysilicon end groups and its application in a nano‐SiO2 aqueous system

In order to improve the dispersity and stability of the nano‐SiO₂ aqueous system with high solid content, a kind of polyacrylic acid dispersant with methoxysilicon end groups (KH590‐PAA) was synthesized by photopolymerization of acrylic acid (AA) initiated with (3‐mercaptopropyl)trimethoxysilane (KH590). After adding KH590‐PAA into the nano‐SiO₂ aqueous dispersion system (20 wt% solid content), the viscosity and the curing time of the system were measured with a rotational viscometer and the inverted bottle method. Moreover, the dispersion mechanism of KH590‐PAA for the nano‐SiO₂ aqueous system was researched by measuring the adsorption capacity, the particle size and the zeta potential of the nanoparticles with a conductivity meter, dynamic light scattering, SEM and TEM, respectively. The results showed that the methoxysilicon groups in KH590‐PAA could react with hydroxyl groups on the surface of nano‐SiO₂ in the process of stirring, which enhanced the adsorption capacity of the dispersant and then increased the surface charge of the particles. Therefore, electrostatic repulsion and steric hindrance effects between the SiO₂ nanoparticles could be further enhanced by adding the KH590‐PAA dispersant, and then the nano‐SiO₂ aqueous system exhibited better dispersity and stability. Besides, the dispersion properties of SiO₂ nanoparticles in water were closely related to the addition amount and the molecular weight of the KH590‐PAA dispersant. © 2018 Society of Chemical Industry     

Stabilization of nano-TiO2 aqueous dispersions with poly(ethylene glycol)-b-poly(4-vinyl pyridine) block copolymer and their incorporation in photocatalytic acrylic varnishes

In this work, TiO₂ nanoparticles were dispersed and stabilized in water using a novel type of dispersant based on tailor-made amphiphilic block copolymers of poly(ethylene glycol)-block-poly(4-vinyl pyridine) (mPEG-b-P4VP) prepared by atom transfer radical polymerization (ATRP). The performance of this new block copolymer as dispersant was compared to a polyelectrolyte dispersant commonly used for TiO₂, sodium salt of polyacrylic acid (Na-PAA). The effect of dispersion technique and type and amount of dispersant on deagglomeration and stability of the TiO₂ aqueous suspensions were studied. After incorporation in a standard waterborne acrylic varnish formulation, dry film transparency, photocatalytic activity, and nanoparticle cluster size were also evaluated. The results show that mPEG-b-P4VP copolymer with appropriate block lengths can have a better performance than Na-PAA in terms of aqueous dispersion stabilization and cluster size reduction in the acrylic matrix. This translates into higher film transparency and photocatalytic performance.     

Preparation of alumina by aqueous gelcasting

The alumina ceramic was prepared by aqueous gelcasting. The effects of zeta potentials, solid loading, dispersant content and milling time on the alumina suspension were studied systematically. The dispersant content has remarkable effects on the viscosity of the suspension. The appropriate dispersant concentration for alumina aqueous slurry with the solid loading of 55 vol.% is 0.6 wt.%. It can be seen that all suspensions (50–56 vol.% solid loading) exhibited a shear-thinning behavior and relatively low viscosity, which was suitable for casting. The degree of shear thinning and the viscosity at high shear rates increased with increasing volume fraction of solid. As the milling time prolongs, viscosity of the suspension decreases first, then the plateau appears and the average diameter keeps changeless. When the milling time was shorter than 20 h, the viscosity of slurries decreased gradually as the time of milling increased. After 20 h milling, the viscosity of the slurry tended to be consistent. Therefore, the ball milling time should be equal to or more than 20 h to obtain a stable suspension at equilibrium. The time available for casting the slurry (idle time) can be controlled by the amounts of initiator and catalyst added to the slurry as well as by the processing temperature. Micrograph of the gelcast green body was homogeneous.     

α-Al2O3-H2O-聚丙烯酸悬浮液流变性的研究

研究了聚丙烯酸(polyacrylic acid,PAA)添加量、固含量和吸附途径对α—Al2O3浆料流变性的影响。实验表明：浆料具有最小粘度时,分散剂添加量存在最佳值。随着固含量提高,浆料最低粘度值提高,分散剂有效添加量范围变窄。吸附途径对浆料的流变性存在一定的影响,在其它条件相同的情况下,低pH值浆料经历非亲合力状态下的吸附,浆料流变性明显改善。     

Novel Coagulation Method for Direct Coagulation Casting of Aqueous Alumina Slurries Prepared Using a Poly(Acrylate) Dispersant

Coagulation of concentrated aqueous alumina slurries prepared using an ammonium poly(acrylate) dispersant by MgO has been studied for direct coagulation casting (DCC). A small amount of MgO (0.2 wt% of alumina) increased the viscosity of the concentrated alumina slurry with time and finally transformed it into a stiff gel. The mechanism of coagulation is proposed such that the time-delayed in situ generation of Mg²⁺ ions from the sparingly soluble MgO forms Mg–poly(acrylate) with the unadsorbed ammonium poly(acrylate) molecules in solution that shift the poly(acrylate) adsorption equilibrium toward the left by depleting the poly(acrylate) molecules adsorbed on the alumina particle surface. This leads to insufficient dispersant coverage on the particle surface and coagulation of the slurry. DCC using MgO is possible only if the slurry is prepared at a dispersant concentration higher than that required for optimum dispersion as the slurries prepared at the optimum dispersant concentration underwent premature coagulation. The gelation time could be tailored within 20 min to a few hours by maintaining the temperature in the range of 70°–30°C. The wet coagulated bodies prepared from 50 vol% alumina slurry showed a compressive strength of nearly 0.05 MPa.