Comparison of dispersants performance on the suspension Lu2O3:Eu stability and high-density compacts on their basis

The conditions for obtaining a stable Lu₂O₃:Eu³⁺ suspension of spherical particles with a diameter of 100 nm using three dispersants possessing an electrosteric stabilizing effect (Dolapix CE 64, Darvan 821 A, Darvan C-N) have been studied. It has been shown that in colloidal processing of ceramics the packing density and microstructure of green bodies can be controlled by regulating the interactions between ceramic particles in the suspension. The influence of the molecular weight and concentration of the dispersant on the stability of Lu₂O₃:Eu³⁺ suspensions containing 5-10 vol.% of the solid loading has been considered. It has been determined that use of Dolapix CE 64 with a concentration of 1 mass.% in the alkaline pH range allows to obtain suspensions with high stability and low viscosity (∼1.7 сP). Such suspensions were used to produce compacts with a maximum relative density of ∼52% and uniform density distribution by the pressure slip casting method. The obtained compacts were densified into translucent Lu₂O₃:Eu³⁺ ceramics by the vacuum sintering method.     

ZTA复相陶瓷凝胶注模成形工艺的研究

本文研究了ＺｒＯ２（３Ｙ）－Ａｌ２Ｏ３复相陶瓷的凝胶注模成形工艺,着重研究了低粘度高固相体积分数浓悬浮体的制备。     

Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles

Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles were investigated. The state of dispersion was evaluated in terms of zeta potential, apparent viscosity and the mean particle size of solid phase in the solution. Zeta potential, apparent viscosity and the mean particle size as a function of pH were performed in absence of dispersant. The result showed that electrostatic stabilization of the aqueous suspension of barite nanoparticles can be accomplished in low acidic and high basic range of pH. In presence of sodium polyacrylate (PAA-Na) dispersant, the isoelectric point (IEP) of the barite nanoparticles was shifted to lower pH and the negative zeta potential was increased in a large range of pH above the (IEP). The optimum amount of PAA-Na dispersant is discussed in the light of zeta potential and viscosity. It is found that the adsorption of PAA is correlated to the net surface charge of the barite nanoparticles and the fraction of dissociated polymer at pH 4, 8.5 and 10. At pH 4, the state of dispersion was achieved at higher amount of electrolyte due to the low fraction of negatively charged dissociated polymer and the positively charge particles. At basic pH, the fraction of dissociated polymer was high and the surface charge of particle was highly negative, therefore, the lowest viscosity was obtained at a small amount of PAA. In addition, the optimum amount of polymer decreased with the increase in pH of the suspension.     

稳定的BaTiO3陶瓷浆料的制备

本文采用胶体"静电位阻稳定机制",以磷酸酯作为分散剂,以沉降高度作为衡量浆料稳定性的参数,研究了BaTiO3粉末的悬浮流变特性及分散剂磷酸酯加入量对BaTiO3浆料稳定性的影响.在最佳pH值和分散剂加入量条件下,制备了高固相含量(50vol%)、稳定性和分散性好的BaTiO3浆料.     

Optimization of Dispersion and Viscosity of a Ceramic Jet Printing Ink

Different amounts (0.5–10.0 wt%) of an oligomeric dispersant were added to a ceramic ink containing 30 vol% of zirconia in butyl acetate. The sediment packing densities of the resulting suspensions were measured. The viscosities of the suspensions were determined using a syringe that was adapted as a capillary viscometer suitable for the measurement of the low viscosities encountered (up to 400 mPas). The highest sediment-packing density coincided with the lowest viscosity and occurred when 1–2 wt% of dispersant, based on the ceramic, was added. Investigation of the supernatant of the suspensions by thermogravimetric analysis indicated that this amount corresponded to the highest level of adsorption of the dispersant on the ceramic. The sediment from this suspension yielded a high density on subsequent sintering.     

The effect of the slurry formulation upon the morphology of spray-dried yttria stabilised zirconia particles

A study has been performed to determine how the characteristics of spray-dried granules prepared from aqueous yttria doped zirconia slurries can be affected by the spray-drying process parameters: dispersant amount, pH and binder type. First, the colloidal stability of aqueous zirconia suspensions as a function of polyacrylic acid content, pH and binder nature has been investigated in order to establish a stability map. The concentration of dispersant required to stabilise the zirconia suspensions decreases with increasing pH (for instance Γ_max=0.93 mg m⁻² at pH 4 and 0.1 mg m⁻² at pH 10). The addition of a binder may modify the state of dispersion. The stability map makes it possible to define regions of stable (dispersed) and unstable (flocculated) suspensions. Then, dried granules have been produced by means of a single droplet drying method. Granules prepared from a dispersed slurry (low Ratio Sediment Height—RSH <53%) result in hollow shapes that contain a single large open pore. Changing the nature of the binder from latex to an hydrosoluble compound (polyvinyl alcohol) has an effect on the wall thickness of the hollow granules. Conversely, granules obtained from a flocculated slurry (high RSH>62%) result in full granules. The sedimentation volume, which represents the state of dispersion of the suspension, is the major factor controlling the droplet drying mechanism.     

Rheology of Zirconia Suspensions in a Nonpolar Organic Medium

Three dispersants (stearic acid, oleic acid, and poly(12-hydroxystearic acid)) are compared for their ability to produce low-viscosity suspensions of zirconia in kerosene. Rheological measurements and sediment packing density measurements show that poly(12-hydroxystearic acid) is a better dispersant than stearic acid or oleic acid; this is explained in terms of the longer tail of the poly(12-hydroxystearic acid) surfactant molecule. The amount of dispersant can be optimized to reduce viscosity and yield point of the suspension, and to eliminate thixotropic hysteresis. The use of a dispersion medium of lower viscosity than the dispersant makes it easy to detect when complete monolayer coverage has been achieved. The loss of pseudoplasticity, brought about by a higher degree of deflocculation, can be recovered by increasing the volume fraction of solids of a suspension and this is beneficial in the plastic forming of ceramics. Rheological measurements showed that these suspensions reach a "critical state" above a critical shear stress (τ_c). This critical state is described by several parameters, i.e., the Bingham yield stress (τ_b), the plastic viscosity (ν_Pl), and the critical shear rate (γ_c), which are dependent on the volume fraction of solids.     

Hydrolysis and Dispersion Properties of Aqueous Y2Si2O7 Suspensions

The dispersion of aqueous γ-Y₂Si₂O₇ suspensions, which contain only one component but have a complex ion environment, was studied by the introduction of two different polymer dispersants, polyethylenimine (PEI) and polyacrylic acid (PAA). The suspension without any dispersant remains stable in the pH range of 9–11.5 because of electrostatic repulsion, while it is flocculated upon stirring due to the readsorption of hydrolyzed ions on the colloid surface. However, suspensions with 1 dwb% PEI exhibit greater stability in the pH range of 4–11.5. The addition of PEI shifts the isoelectric point (IEP) of the suspensions from pH 5.8 to 10.8. Near the IEP (pH_IEP=10.8), the stability of the suspensions with PEI is dominated by the steric effect. When the pH is decreased to acid direction, the stabilization mechanism is changed from steric hindrance to an electrosteric effect little by little. PAA also has the effect of reducing the hydrolysis speed via a "buffer effect" in the basic pH range, but the lack of adsorption between the highly ionized anionic polymer molecules and the negative colloid particle surfaces shows no positive effect on hydrolysis of colloids and on the stabilization of Y₂Si₂O₇ suspensions.     

On the preparation of organosilanized silicon carbide aqueous suspension

The functionalization of ceramic nanoparticles with organosilanes is commonly employed to improve the surface adhesion mechanism for specific applications, especially in polymer composites. However, this surface modification changes the behavior of the nanoparticles in suspension, which is important for applications that require preparation involving aqueous medium. In the present study the influence of organosilanization on the size and stability of SiC particles in aqueous medium was evaluated. Initially, SiC particles were organofunctionalized using (3-aminopropyl) triethoxysilane through two different reaction routes (SiC_{Sil I} and SiC_{Sil II}). XPS spectroscopy of solid particles showed higher content of nitrogen atoms arising from the organosilanization reaction in the SiC_{Sil II}, prepared in ethanol. Compared to the unmodified SiC aqueous suspension, the organosilanized SiC aqueous suspensions presented much higher particle sizes, with the largest particle size distribution, assigned mainly to the organosilanization of SiC agglomerates. Subsequently, polyethylenimine (PEI) was tested as a dispersant for the aqueous suspensions, aiming to increase the repulsion forces among the particles and induce their de-agglomeration. The addition of PEI to SiC and SiC_{Sil II} particle aqueous suspensions resulted in a drastic reduction in the particle size (up to 40% (D50) at pH 5.5) and narrowest particle size distribution over a wide pH range. This fact was attributed to the PEI electrosteric effect on aqueous suspensions containing SiC or SiC_{Sil II}, which was supported by dynamic laser scattering and zeta potential results.     

Direct coagulation casting of YSZ powder suspensions using MgO as coagulating agent

Direct coagulation casting (DCC) of aqueous 8 wt% yttria stabilized zirconia (YSZ) powder suspensions prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Small amount (<0.1 wt% based on YSZ) of MgO powder dispersed in the YSZ powder suspension at ∼5 °C set the suspension in to stiff wet-coagulated body when exposed to room temperature (30 °C) due to the reaction between ammonium poly(acrylate) and MgO. MgO concentration equivalent to react with dispersant did not coagulate the YSZ powder suspension though it precipitate the whole ammonium poly(acrylate) dispersant as Mg-poly(acrylate). This is because of the ability of the YSZ powder to disperse in water at alkaline pH (∼9.5) without any dispersant by electrostatic mechanism. The YSZ powder suspensions form stiff coagulated bodies at MgO concentration double or more of the equivalent amount required for reacting with the dispersant. Setting of the YSZ powder suspension is due to the heterocoagulation of the YSZ particles and MgO particles added in excess of the equivalent amount to react with the dispersant, having opposite surface charges. The wet-coagulated body showed relatively high compressive yield strength (155 kPa) and Young’s modulus (3.1 MPa). The green bodies prepared by humidity controlled drying of the wet-coagulated bodies sintered to >98% TD at 1550 °C.     

Electrosteric stabilization of concentrated cement suspensions imparted by a strong anionic polyelectrolyte and a non-ionic polymer

Strong polyelectrolytes, known as superplasticizers, improve the initial fluidity of concentrated cement suspensions through electrostatic stabilization. These polyelectrolytes do not maintain the initial fluidity, however, primarily due to an increase in the ionic strength of the cementitious suspension. Consequently, non-ionic polymers are often used in conjunction with polyelectrolytes to provide steric stabilization and hence to sustain the desired fluidity over a longer time, and this has lead to the development of copolymers with both electrostatic and steric (electrosteric) functionalities. To design such polymers, it is necessary to optimize the balance between electrostatic and steric stabilization to maximize suspension fluidity. We have quantified the effects of a strong anionic polyelectrolyte, melamine formaldehyde sulfonate (MFS), and a non-ionic polymer, hydroxypropylmethylcellulose (HPMC), on the zeta potential of cement particles and the steady shear and low-amplitude rheological properties of concentrated cement suspensions. While the adsorption of MFS onto the cement particle surfaces leads to a sign inversion in the zeta potential, the adsorption of the non-ionic HPMC has no significant effect on the potential. The addition of HPMC to the suspensions substantially reduces the steady shear viscosity and the storage modulus at constant MFS concentration; in addition, there exists an intermediate HPMC concentration that minimizes fluidity. The resulting suspension fluidity is also maintained over a longer time than in the absence of HPMC. This improvement in the stability and fluidity of cement suspensions is attributed to “complementary electrosteric dispersion/stabilization”, and provides insight to the design of polymers with electrosteric functionality.     

Printing of NiO-YSZ nanocomposites: From continuous synthesis to inkjet deposition

Water-based inks, containing nanometric NiO and YSZ particles in 66/34 vol. % ratio, are produced by colloidal stabilization of a binary dispersion obtained via continuous hydrothermal synthesis at supercritical conditions, i.e. 280 bar and 400 °C. The method yields single-crystal particles with diameter ≤ 10 nm for both phases in a single-step process, achieving a highly mixed composite. Two different approaches are applied to formulate inks printable with piezoelectric printheads, i.e. an electrostatic and an electrosteric stabilization path. The use of an electrosteric dispersant results in colloids with superior stability > 200 days, more uniform thin films and finely nanostructured porous cermet films with thickness below 500 nm, after reducing NiO to Ni. Particles coarsening to 50–150 nm is obtained at 1000 °C, accompanied by a shrinkage of ca. 43% in thickness without the formation of cracks or delamination of the zirconia substrates.     

Aqueous and Nonaqueous Colloidal Processing of Difficult‐to‐Densify Ceramics: Suspension Rheology and Particle Packing

Aqueous and nonaqueous colloidal processing of zirconium diboride (ZrB₂) and boron carbide (B₄C) has been investigated. The aqueous and nonaqueous ZrB₂ and B₄C suspension formulations have been optimized. The suspensions were cast into green bodies using slip casting. The correlation between the state of dispersion with the rheological properties of the suspensions and the resulting packing density was observed in both aqueous and nonaqueous processing. The attractive interactions between powder particles in water were difficult to overcome with electrical double layer or electrosteric repulsion. Reasonably low viscosity aqueous ZrB₂ suspensions up to 45 vol% solids could be prepared. It was not possible to produce low viscosity (viscosity below 1 Pa·s at shear rate of 100 s^?1) aqueous B₄C suspensions with solid content above 30 vol%. Slip casting of the weakly aggregated ZrB₂ suspensions resulted in low packing densities (~55% relative density) of the green bodies. On the other hand, dispersion of powder particles in nonaqueous media (cyclohexane and dodecane) enabled suspensions with lower viscosities and a higher maximum solid concentration (up to 50 vol%) to be prepared. The well‐dispersed nonaqueous suspensions promoted an efficient particle packing, resulting in higher green densities (64% and 62% relative density for ZrB₂ and B₄C, respectively) compared to aqueous processing. The significantly high green densities are promising to allow densification of the materials at lower sintering temperature.     

Electrostatic and electrosteric stabilization of aqueous slips of 3Y–ZrO2 powder

Yttria-doped zirconia powder (3Y-ZrO₂) was characterized and dispersed in distilled water. The state of dispersion was evaluated in terms of zeta potential, apparent viscosity and the mean particle size of solid phase in the slip. Zeta potential, apparent viscosity and the mean particle size as a function of pH indicated the pH range of electrostatic stabilization. These results showed that electrostatic stabilization of the slip can be accomplished in low acidic and high basic range of pH. Dissolution of yttria from the powder surface in acidic pH was found to be high and fast, risky to the stability of the slip as well as the microstructure of the sintered body. Electrosteric stabilisation by addition of an anionic polyelectrolyte (PMAA-NH₃) shifted the isoelectric point (IEP) to lower pH. The state of dispersion was further investigated by particle size measurements of the solid phase in the slip. The optimum amount of dispersant is discussed in terms of zeta potential and viscosity. The adsorption of polyelectrolyte is considered at pH 4, native pH of suspension and at pH 10, below and above the IEP of powder and correlated with the dissociation rate of polymer and the net surface charge of particles at given pH. Higher adsorption of dissociated polymer to the positively charged surfaces justifies the higher optimum amount of polyelectrolyte at pH 4.     

稳定的SrTiO3陶瓷浆料的制备

本采用胶体“电空间稳定机制”，以PMAA-NH4为分散剂，以沉降高度作为衡量浆料稳定性的参数，研究了SrTiO3粉末的悬浮流变特性及分散剂PMAA-NH4加入量对SrTiO3浆料稳定性的影响。在最佳pH值和分散剂加入量条件下，制备了高固相含量（50vol%)，稳定性和分散性好的SrTiO2浆料。     

Using a Brush Copolymer as Efficient Dispersant for the Preparation of Highly Stabilized Ag Nanoparticles in Aqueous Suspensions

Silver (Ag) nanoparticle has extremely high surface energy and it is difficult to find an efficient dispersant to prevent its agglomeration in suspensions. A new brush copolymer, succinic anhydride modified epoxy-amine poly[(propylene oxide)-co-(ethylene oxide)]-grafted polymer (EPOA), which can efficiently disperse concentrated aqueous suspensions of Ag nanoparticles is revealed. The dispersion efficiency of EPOA for the dispersion of a 60 nm-Ag nanoparticles in aqueous suspension is studied by measuring its sedimentation and rheological behavior, and the results are compared with those of a commercially available dispersant, ammonium poly(acrylic acid) (PAA-NH₄). Interactions between the dispersants and the Ag nanoparticles are characterized by zeta potential and adsorption analyses. Theoretical calculations are conducted to clarify the adsorption and the dominant dispersion stabilization mechanisms of the dispersants. Compared with PAA-NH₄, EPOA obtains a higher stable suspension of Ag nanoparticles with less significant sedimentation over 1 month. The dispersion homogeneity of the suspension remains excellent even at an extremely high solid loading of 30–40 wt%. According to adsorption analysis, it is suggested that both EPOA and PAA-NH₄ adsorb via single-point attachment through the carboxyl group on the Ag surface. Based on theoretical calculations, the Ag nanoparticles are better stabilized by EPOA via an electrosteric dispersion mechanism.     

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.     

Effect of dispersant on chain formation capability of TiO2 nanoparticles under low frequency electric fields for NO2 gas sensing applications

In this study, the effect of Dolapix CE64 as dispersant on the deposition mechanism and chain formation of TiO₂ nanoparticles in the different frequencies under non-uniform AC electric field was investigated. The optical microscope (OM) images of the deposition patterns obtained at the frequency of 1 Hz and 100 Hz in non-aqueous media one containing dispersant and the other being dispersant free revealed that the addition of charge inducing agents (dispersant) has drastically changed deposition mechanism enabling particles to enter the gap leaving the electrodes surfaces uncoated. At 10 kHz, it was observed that by the introduction of Dolapix CE64 the TiO₂ nanoparticles were able to form chain-like patterns along the electric field lines bridging the interelectrode gap. The obtained pearl chain formation (PCF) was employed to fabricate an NO₂ gas sensor which showed a good response to the target gas at 450, 500 and 550 ˚C.     

The use of polyelectrolyte stabilisers for suspension polymerisation: the effect of pH on particle size distribution

Ammonium polymethacrylate (APMA) and sodium polymethacrylate (PMA‐Na) were used as suspending agents for the suspension polymerisation of methyl methacrylate (MMA). The effect of pH on particle sizes and the stabilisation mechanism were examined. Increasing the pH caused a decrease in the particle sizes, and the formation of fine particles with diameters smaller than 10 µm. The amount of suspending agent required to stabilise a monomer dispersion and to prevent coalescence during suspension polymerisation decreases with increasing pH. The prevailing stabilisation mechanism that governs the dispersion stability is probably the electrosteric mechanism. Copyright © 2006 Society of Chemical Industry     

纳米TiN粉末在水溶液和无水乙醇中的分散行为

通过粒径和颗粒表面电性质的测定,探讨了纳米TiN粉末在水溶液和无水乙醇中的分散特性及表面活性剂对分散的影响. 实验结果表明,纳米TiN颗粒在水中分散,溶液的pH值对颗粒的分散性有很大的影响,在pH 8处,能得到最好的分散效果. 随pH值变化,颗粒表面的荷电性质从正变化为负,等电点为3.7. 其分散行为遵循双电层静电稳定机制. 纳米TiN颗粒在无水乙醇中的分散行为受pH值的影响相对较小. 在整个pH范围内,颗粒表面荷正电,颗粒表面的溶剂化作用对分散起主导作用. 表面活性剂聚氧乙烯十二烷基醚可作为纳米TiN颗粒在水溶液中分散的分散剂,聚乙二醇可作为在水溶液和无水乙醇中分散的分散剂.