Dispersion of Colloidal Alumina using a Rhamnolipid Biosurfactant

Dispersability of colloidal alumina in water has been studied using a rhamnolipid containing biosurfactant. Zeta potential measurements revealed that the surface charge of alumina was altered due to adsorption of the biosurfactant and the iso‐electric‐point of alumina shifted from pH 9 to 6.3. Sedimentation tests indicated that the alumina suspension was completely dispersed for 3–5 hours in the presence of biosurfactant after which some settling was observed. Stability of the suspension in the time period studied was found to be independent of pH. Capillary suction time measurements showed that the alumina suspension was dispersed in the presence of the biosurfactant and varied with pH. Maximum dispersion is obtained in the pH range of 3.5–5 and 7–11 while a minimum is obtained around pH 6. This behavior is consistent with the changes in zeta potential in the presence of the biosurfactant and thus capillary suction time measurements appeared to be more reliable than the sedimentation tests. Optimization studies showed that about 60 mg/g of biosurfactant was necessary for best dispersion and dispersion could be done up to 40% solids. The application of a natural biosurfactant for dispersing colloidal alumina has been demonstrated.     

Agglomeration of alumina submicronparticles by silica nanoparticles: application to processing spheres by colloidal route

In aqueous media, heterocoagulation between submicronic alumina (400 nm) and nanometric silica (25 nm) leads to the adsorption of silica on the alumina surface. By controlling the coverage rate of alumina particles, this adsorption destabilizes the suspension that leads to a very porous network of agglomerated particles. This work shows that the structure is all the more open as the density of charge carried by the two oxides is high and the ionic strength in the suspension low. From such a flocculated suspension, a new colloidal process to fabricate ceramic spheres is proposed which is based on a size increase of agglomerates. Under a controlled rotation of the vessel, electrostatic attraction between the surface charges of opposite polarity induces a size increase of agglomerates until the formation of spheres occurs. It has been shown that the mechanism of growth is poisoned by species adsorbed such as ions. Nevertheless, this new process proves very promising because it leads to a narrow size distribution of spheres by colloidal way, which can be subsequently consolidated by sintering, with a smooth surface.     

Stability of dispersions of colloidal alumina particles in aqueous suspensions

The colloidal stability of suspensions of alumina particles has been investigated by measuring particle size distribution, sedimentation, viscosity, and zeta potential. Alumina particles were found to be optimally dispersed at pH around 3 to 7.8 without dispersant and at pH 8.5 and beyond with dispersant. The above results corroborate zeta potential and viscosity measurement data well. The surface charge of alumina powder changed significantly with anionic polyelectrolyte (ammonium polycarboxylate, APC) and the iep shifted toward more acidic range under different dispersant conditions. It was found that the essential role played by pH and dispersant (APC) on the charge generation and shift in the isoelectric point of alumina manifests two features: (i) the stability decreases on approaching the isoelectric point from either side of pH, and (ii) the maximum instability was found at pH 9.1 for alumina only and at pH 6.8 for alumina/APC, which is close to the isoelectric points for both the system, respectively. Using the model based on the electrical double-layer theory of surfactant adsorption through shift in isoelectric points, the authors could estimate the specific free energy of interaction (7.501 kcal/mol) between particles and dispersant. The interaction energy, zeta potential, sedimentation, and viscosity results, were used to explain the colloidal stability of the suspension.     

胶溶法制备改性氧化铝的结构及织构特点

对胶溶法制备的镧和聚乙二醇(PEG)改性的氧化铝载体进行了深入研究.     

Preparation and characterization of biodegradable poly(isobutylcyano acrylate) nanoparticles with the surface modified by the adsorption of proteins

The purpose of this work was to develop and characterize a biodegradable colloidal drug carrier which avoids uptake by the mononuclear phagocyte system. In order to imitate the cell surface, a sialic-acid-rich glycoprotein (human orosomucoid) was adsorbed onto poly(isobutylcyano acrylate) nanoparticles. The adsorption of human serum albumin and asialo-orosomucoid was also tested as a control. The adsorption was found to be dependent on the pH value and reached its maximum at a pH value close to the isoelectric point (pI) of each protein. The increase in the ionic strength due to the addition of NaCl generally resulted in an increase in the amount adsorbed. Considering the amounts of protein adsorbed (maximum of 4.5 mg m⁻²), the adsorption was assumed to be of the monolayer type. The adsorption kinetics performed at the pI of each protein showed that the equilibrium was reached within 1 h for albumin and within 8 h for the two glycoproteins. This significant difference suggested that conformational rearrangements could be much slower for the two glycoproteins than for the non-glycosylated albumin. The protein layer was found to be stable at pH 7 when the adsorption was performed beforehand at the pI, i.e. at an acidic pH. Finally, using hydrophobic interaction chromatography, the surface of the coated nanoparticles was found to be much more hydrophilic than the surface of the unmodified nanoparticles.     

Polysaccharide-modified iron oxide nanoparticles as an effective magnetic affinity adsorbent for bovine serum albumin

The magnetic separation technique based on magnetic iron oxide nanoparticles (MNPs) has potential applications in protein adsorption and purification, enzyme immobilization, cell sorting, nucleic acid detachment, and drug release. However, the naked MNPs are often insufficient for their hydrophilicity, colloidal stability, and further functionalization. To overcome these limitations, chitosan was firstly carboxymethylated and then covalently conjugated on the surface of the MNPs ranging in size from about 5 to 15 nm, which were prepared by co-precipitating iron (II) and iron (III) in alkaline solution and then treating under hydrothermal conditions. It was found that such modification did not result in the phase change of the MNPs, and the resultant modified nanoparticles were still superparamagnetic. In particular, the colloidal stability of MNPs in aqueous suspension was improved after the surface modification. By investigating the adsorption of bovine serum albumin (BSA) on the modified MNPs, it was observed that the adsorption capacity of the BSA on the modified MNPs increased rapidly within several minutes and then reached the maximum value at about 10 min. The adsorption equilibrium isotherm could be fitted well by the Langmuir model. The medium pH affected greatly the adsorption of the BSA. The maximum adsorption of the BSA occurred at the pH value close to the isoelectric point of the BSA, with a saturation adsorption amount of 94.45 mg/g (25 °C). For the BSA feed concentration of 1.017 mg/ml, a high desorption percentage of 91.5% could be achieved under an alkaline condition (pH 9.4).     

Correlation between Dispersion Stability of Concentrated Ceramic Suspension and Capillary Suction Time

Dispersion stability of highly concentrated ceramic suspensions using different dispersants required for colloidal processing can be assessed by measuring capillary suction time (CST). A systematic evaluation of dispersibility characteristics of colloidal alumina suspension is reported in the presence of three commonly used dispersants, namely, Dispex N 100, Darvan C, and Aluminon by employing the CST technique. The correlation between dispersibility of ceramic suspension and capillary suction time has been established. It has been found that higher the CST value of a suspension, the greater is the stability of the suspension and viceversa. In this investigation, this technique is employed both to choose suitable dispersant and to characterize the suspension. It has been concluded that higher the dispersion ratio (DR) of a suspension above unity the better is the stability and the lower the DR value below unity, the better is the aggregation tendency of the suspension. Quantitative estimation of dispersibility of an aqueous suspension is reported in terms of dispersion ratio. The CST technique has been found to be very useful and suitable for obtaining information for assessing stability of ceramic suspensions and characterizing concentrated ceramic slurry.     

SUSPENSION PROPERTY OF ALUMINA IN LAPPING MEDIA

In order to understand the suspension properties of alumina grit in lapping liquids, with particular interest on their flocculation behavior both electro kinetic and sedimentation experiments were carried out on three different alumina powders, that were either wet or air classified in two commercial additives ( Mon - 60 and Rust Lick - 900 ). The results suggest that all three alumina powders have some acidic surface impurity and both Mon - 60 and Rust Lick - 900 are adsorbed on the alumina surface below pH 9. The sedimentation behavior of these alumina powders from their dispersions is independent of the classification of the alumina and nature of the additive but is dependent on the pH of the dispersion.     

Hydrated alumina surface treatment on a titanium dioxide pigment: changes at acidic and basic pH

Amphoteric, inorganic particles used as pigments and extenders in dried coatings are not completely inert, particularly when exposed to acidity similar to atmospheric pollution, or when in a water-borne paint suspension at alkaline pH. Changes to these materials may harm the integrity of the dried coating and thus its performance during weathering or affect the colloidal stability during storage within liquid paint. The effect on aqueous titanium dioxide pigment suspensions was examined under various pH conditions. A substantial amount of aluminum was dissolved, but little silicon or titanium. Dissolution occurred at both acid and alkali pH leaving a different balance of hydrated alumina phases and overall surface composition. Changes in particle surface were apparent in topography, colloidal properties and by thermogravimetry. Such changes show that other, more complicated, changes may be possible, particularly in an aqueous paint medium where there are many other ingredients in solution or suspension.     

Smooth model cellulose I surfaces from nanocrystal suspensions

Removal of lignin, hemicelluloses and other minor components during pulping results in a porous fibrillar structure. Interactions of cellulose fibre surfaces with wet-end additives and other materials depend both on the interfacial properties of the cellulose and on the morphology of the surface. It would be useful to be able to separate the interactions with the cellulose from those that depend on surface roughness and porosity by preparing flat cellulose surfaces. Current methods give surfaces of amorphous cellulose or of cellulose II, differing in density and crystallinity from the original cellulose I surface. We propose a new route to prepare smooth model surfaces of cellulose I, starting from colloidal dispersions of cellulose I nanocrystals. The nanometer-sized width of these rod-like colloidal particles allows a relatively flat surface to be prepared from the suspension by casting an aqueous suspension on an appropriate surface and allowing the water to evaporate. Oriented films can be prepared by spin-coating or shearing. The surface composition and morphology of the films were examined by X-ray photoelectron spectroscopy and atomic force microscopy.     

A prediction method for the isoelectric point of binary protein mixtures of bovine serum albumin and lysozyme adsorbed on colloidal titania and alumina particles

Bovine serum albumin and lysozyme mixtures of different mole fractions were adsorbed to colloidal alumina (116 nm) and titania particle (271 nm) suspensions of 2 vol % solid content for 16 h at pH 7.5. The total protein amount normalized to the powder surface area was 1000 ng/cm2. The zeta potential of the protein-treated suspensions was measured as a function of pH and the isoelectric point (IEP) obtained. A simple prediction model in two refinement steps was derived and evaluated for the obtained IEPs. The best model fit which takes into account moles of protein and surface fractions yielded an average prediction error of 7.5% and a maximum error of 16.7%.     

Bovine serum albumin adsorption onto colloidal Al2O3 particles: a new model based on zeta potential and UV-vis measurements

We investigated the adsorption of bovine serum albumin (BSA) on colloidal Al2O3 particles in an aqueous environment. Changes in the zeta potential of the Al2O3 particles upon the adsorption of BSA were measured using an electro-acoustic technique. The mass of protein adsorbed was determined by using UV-vis spectroscopy. The change of the isoelectric point of the Al2O3 powder-protein suspension was found to be a function of adsorbed protein mass. It was shown that approximately one monolayer of BSA was needed to fully mask the surface and to compromise the charge of Al2O3. From titration experiments it follows that about 30-36% of the negatively charged groups of the protein form bonds with the protonated and charged Al2O3 surface. On the basis of our observations we introduced a new adsorption model for BSA on Al2O3 particles.     

Preparation and characterization of polymer single crystals for use as adsorbent

Single crystals of polyoxymethylene are flat, homogeneous, and essentially uncharged and offer a large specific surface area. Since they can be prepared reproducibly and in large amounts, they constitute a suitable model substrate in systematic adsorption studies. The crystallization procedure is discussed in some detail. The thickness of the crystals is obtained from EM and SAXS measurements, the results being in excellent mutual agreement. Combining this thickness with the crystal density the geometrical surface area is found to be 150 m²/g. This is compared with the surface area obtained by BET analysis of nitrogen adsorption (30 m²/g) and with the surface area that follows from adsorption of polyoxyethylated nonyl phenols from aqueous solution (60 m²/g). The discrepancy in the results is explained in terms of different degrees of aggregation of POM crystals in the dry state and in suspension. Finally, some preliminary results of albumin and sodium polystyrene sulfonate adsorption are discussed.     

Influence of poly(ethylene oxide) brushes on the rheological properties of MgO colloidal suspensions in water

A combined experimental and multiscale simulation study of the influence of polymer brush modification on interactions of colloidal particles and rheological properties of dense colloidal suspensions has been conducted. Our colloidal suspension is comprised of polydisperse MgO colloidal particles modified with poly(ethylene oxide) (PEO) brushes in water. The shear stress as a function of shear rate was determined experimentally and from multiscale simulations for a suspension of 0.48 volume fraction colloids at room temperature for both bare and PEO-modified MgO colloids. Bare MgO particles exhibited strong shear thinning behavior and a yield stress on the order of several Pascals in both experiments and simulations. In contrast, simulations of PEO-modified colloids revealed no significant yielding or shear thinning and viscosity only a few times larger than solvent viscosity. This behavior is inconsistent with results obtained from experiments where modification of colloids with PEO brushes formed by adsorption of PEO-based comb-branched chains resulted in relatively little change in suspension rheology compared to bare colloids over the range of concentration of comb-branch additives investigated. We attribute this discrepancy in rheological properties between simulation and experiment for PEO-modified colloidal suspensions to heterogeneous adsorption of the comb-branch polymers.     

Polyvinylpyrrolidone adsorption and structural studies on homoionic Li-, Na-, K-, and Cs-montmorillonite colloidal suspensions

Structural aspects of dilute homoionic Li-, Na-, K-, and Cs-montmorillonite (M-montmorillonite) particle suspension (1 g/L) under low-electrolyte-concentration (0.1 mM MCl) conditions were characterized by static (absorbance or turbidity) and dynamic (photon correlation spectroscopy) light-scattering methods as well as by the adsorption behaviors of nonionic polyvinylpyrrolidone (PVP) mol wt 5,000 g/mol (LMW PVP) and mol wt 400,000 g/mol (HMW PVP). Taking Li-montmorillonite as a reference for a single plate particle, a particle size increase and a surface accessibility decrease to polymer adsorptions were measured along the Li, Na, K, and Cs series. The results are related to the existence of montmorillonite quasicrystals or tactoids in diluted suspension, whose stability increases along the same cation series. Molecular weight effects on the PVP surface accessibility are discussed in terms of permeation properties of the different M-montmorillonite particles. Modeling the results calculates an average number of plates in montmorillonite quasi-crystals and the surface area distribution of ultramicropores <0.7 nm and pores >0.7 nm in M-montmorillonite particles. It can also be demonstrated by applying hydrodynamic and electrokinetic methods that the measured high absorbance or turbidity increase of PVP-loaded montmorillonite particles is not due to aggregation phenomena but to a PVP contribution in the light-scattering intensity.     

二次乳化法(W/O)/W制备蛋白质流通色谱固定相的研究

以甲基丙烯酸缩水甘油酯为单体,二甲基丙烯酸乙二醇酯为交联剂,甲苯与正庚烷为有机致孔剂,20%的甘油水溶液为内水相(超孔致孔剂),利用二次乳化法制备了(W/O)/W乳液,通过紫外光引发悬浮聚合生成两类孔型高分子微球(BiPB).BiPB孔径为双峰分布,范围分别在10~100nm和1000~7300nm之间;而其体积平均粒径、比表面积、湿密度、静态吸附容量与不含超孔的微孔介质(MiPB)接近.修饰相同二乙胺密度的BiPB和MiPB介质虽在较低流速(5cm/min)下有相近的动态吸附容量,但在高流速(40cm/min)下BiPB的动态吸附容量约为MiPB的动态吸附容量的3倍,表明BiPB介质的超孔结构对孔内传质的强化作用,因而其更适合于高速的蛋白质色谱分离.     

Polyphosphate interaction with aluminium-doped titania pigment particles

The interaction of a widely used Calgon™ polyphosphate dispersing reagent with aluminium-doped titania pigment particles has been investigated using electrokinetic and rheological studies combined with adsorption isotherms. The influence of pH, aluminium dopant concentration and polyphosphate concentration is reported. Polyphosphate adsorption density and affinity with the titania pigment surface is highest under acidic solution conditions. This however, does not necessarily transfer to enhanced dispersion properties at low pH values. At pH 9, the polyphosphate adsorption density correlates directly with a reduction in pigment particle interactions making polyphosphate an effective titania pigment dispersant under alkaline conditions. Conversely, at pH 4, polyphosphate adsorption densities less than 0.1 mg m⁻² have no effect on the colloidal stability of the titania particles and their Newtonian flow behaviour. At adsorption densities of 0.1 mg m⁻², approaching the iep (near 0.2 mg m⁻²), the suspension aggregates. It is not until the polyphosphate adsorption density is greater than 0.3 mg m⁻² that the titania pigment suspension begins to restabilise. It is proposed that chemisorption dominates polyphosphate adsorption at pH 9 whilst at pH 4 a combination of chemisorption and electrostatic adsorption occurs. Stabilisation by the polyphosphate present at the pigment surface depends on both electrostatic and steric effects. At high pH, both are effective but at low pH, electrostatic stabilisation is partly neutralised and higher adsorption densities are required for effective stabilisation.     

The Synthesis of Stable, High Solid Content Alumina Sol

The stable alumina sol with an ASB/water molar ratio of 1:30 could not be obtained via the general peptization process because gelation occurred immediately. With the addition of EAcAc the stability of this sol was greatly improved. The studies using TEM, UV-V is and IR spectra revealed that a surface modification layer was formed around the Al₂O₃ colloidal particle through the chelating reaction of EAcAc with the surface HO-Al groups. The Al₂O₃ colloidal particles were therefore sufficiently capped and the growth of the colloidal particles was effectively prevented.     

Slowly Removing Surface Ligand by Aging Enhances the Stability of Pd Nanosheets toward Electron Beam Irradiation and Electrocatalysis

Surface ligands play an important role in shape-controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well-preserved morphology, together with significantly enhanced stability toward both e-beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re-exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect-rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.     

Interactions and dispersion stability of aluminum oxide colloidal particles in electroless nickel solutions in the presence of comb polyelectrolytes

The effect of comb polyelectrolytes on the dispersion stability of colloidal alumina particles in DI water and commercial electroless nickel (EN) solutions was investigated. Adsorption of polyelectrolytes and major EN components onto colloidal alumina was assessed by TGA, chemical analysis, and zeta potential measurements. Zeta potential measurements were made during titrations of comb-polyelectrolyte-stabilized dispersions with EN solutions to full ionic strength for the first time. The compilation of titration curves made with varying amounts of comb polyelectrolytes provides high resolution and novel insight into the particle/surfactant/EN systems. Continuous decrease in particle/EN components surface interactions with the increase in comb polyelectrolyte coverage is observed. Laser diffraction measurements reveal steric stabilization of nano- and submicronmeter alumina dispersions in both DI water and EN solutions with >7 wt% and >2 wt% comb polyelectrolyte, respectively.