Investigations of flocculation possibilities of the water alumina suspension in the presence of nonionic polymer

The effect of solution pH and molecular weight of polyethylene glycol (PEG) and polyethylene oxide (PEO) on their adsorption as well as stability of the colloidal Al₂O₃ water suspension was studied. The following methods were applied: turbidimetry, spectrophotometry, viscosimetry, potentiometric titration and microelectrophoresis.It was shown that the increasing solution pH affects conformation of the adsorbed macromolecules which affects the stability properties of such systems. The polymer adsorption causes deterioration of the stability conditions of the investigated alumina systems in comparison to those without polymer at all investigated pH values. At pH 3 and 6 the effect of the suspension destabilization is significantly smaller than at pH 9. The most effective flocculent of Al₂O₃ water suspension is PEO of the molecular weight 218,000 at pH 9.     

Effect of Polymer Dispersant Structure on Electrosteric Interaction and Dense Alumina Suspension Behavior

The present paper reports on research on the effect of molecular structure of polymer dispersants on the relationship between the electrosteric interaction of dispersants on solid surfaces and the viscosity of suspensions. Ammonium polyacrylate with different hydrophilic to hydrophobic ratios ( m:n ) was prepared and added to dense Al₂O₃ suspensions (40 vol%). The steric interactions and adsorbed structures of dispersants on Al₂O₃ powders were examined under an atomic force microscope (AFM). An optimum hydrophilic to hydrophobic group ratio, which was obtained from the maximum repulsive force and the minimum viscosity of suspension, was determined at m :n = 3:7. The changing mechanism of the adsorbed structure and the steric interaction of dispersants and the suspension viscosity by the hydrophilic to hydrophobic molecular ratio were discussed by comparing the experimental force curve and DLVO theory.     

Spray-drying of ceramics for plasma-spray coating

The spray-drying process of ceramics which are candidate materials for thermal barrier coatings (TBCs), i.e. 3YSZ+0, 2, 4, 6 wt.% Al₂O₃, is discussed in this paper. The two most important properties of spray-dried powders to determine the coating quality are density and particle size. Polyethyleneimine (PEI) acts as both an organic binder and a dispersant giving low viscosity in the suspension. The optimised suspension composition is: ⩾ 33.6 vol.% powder+1.8 wt.% PEI+ethanol, and operational parameters of the spray-dryer: drying temperature 175°C, feeding rate 55 cm³/min, feeding pressure 1.013×10⁴ Pa.     

POEGMA‐b‐PAA comb‐like polymer dispersant for Al2 suspensions

POEGMA‐b‐PAA comb‐like polymer is synthesized through RAFT polymerization, and it is employed as an efficient dispersant for Al₂O₃ suspensions. The POEGMA‐b‐PAA polymer consists of PAA chains and POEGMA comb‐like chains. The former provide electrostatic attraction between Al₂O₃ particles and polymer, while the latter extend to solution and maintain the stability of suspension due to strong steric hindrance. The adsorption is proven and the rheology behaviors of Al₂O₃ suspensions are strongly improved. Different POEGMA‐b‐PAA polymers with different length of side chains have similar but not identical rheological properties. The polymer with the appropriate length of side chain provides the biggest improvement to rheological properties of Al₂O₃ suspensions, such as apparent viscosity and granularity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43352.     

Electrophoretic shaping of sub-micron alumina in ethanol

The electrophoretic deposition (EPD) method was used to shape sub-micron Al₂O₃ green body in ethanol. The uniformity of the final deposit was affected by the colloidal properties of the suspension. Therefore, the stability of Al₂O₃ suspension in ethanol was studied in terms of electrophoretic mobility, viscosity and conductivity. The EPD kinetics were further investigated with different electrical conditions. The effect of cellulose acetate membrane on deposit was also studied. The green body with a relative density of about 60 %TD was associated with a narrow pore size distribution, indicating a high homogeneity of particle coordination. After presintering and HIPing at 1250 °C, a fully dense alumina ceramic was obtained with an average grain size of 0.65 μm.     

Phase separation of poly(ether sulfone imide) modified epoxy resin

Poly(ether sulfone imide)s (PEI) with molecular weight M_n ∼ 10⁴ were synthesized from 3,3′,4,4′-benzophenone tetracarboxylic dianhydride and amine terminated poly(ether sulfone) having molecular weights ranging from M_n ∼ 400 to M_n ∼ 4000. Thus, the PEIs had the same molecular weight but various imide and ether sulfone contents. The PEIs were mixed with a stoichiometric mixture of diglycidyl ether bis-phenol-A (DGEBA)/diamino diphenyl sulfone (DDS). The effect of PEI on the curing reaction of DGEBA/DDS and the morphology of the polymer blend were studied by differential scanning calorimetry (DSC) and optical microscopy. In the DGEBA/DDS/PEI blend with a fixed PEI molecular weight and PEI concentration but with various imide content, the experimental data revealed the PEI with a higher content of ether sulfone had a lower T_g and a better compatibility with solvents and epoxy resins; the curing reaction rate of DGEBA/DDS/PEI was faster for PEI with a higher imide content; the DSC data of cured DGEBA/DDS/PEI showed two T_gs, indicating phase separation between PEI and cured epoxy resins; and the data of optical microscopy showed that the compatibility of PEI with epoxy resins increased with the content of ether sulfone in PEI. © 1996 John Wiley & Sons, Inc.     

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.     

Yield stress of oxide dispersions—intermolecular forces of adsorbed small ionic additives and particle surface roughness

The yield stress‐pH and zeta potential‐pH behaviour of α‐alumina and zirconia dispersions with adsorbed small ionic molecular additives such as phosphate and pyrophosphate were determined. The result for adsorbed citrate was included for comparison. Adsorbed phosphate at high surface coverage increased the maximum yield stress of low surface area α‐Al₂O₃ (AKP30 and AA07) dispersions slightly. This increase is attributed to the intermolecular hydrogen bonding between phosphates adsorbed on interacting particles. With high surface area ZrO₂ (Tosoh) dispersions, however, the adsorbed phosphate decreased the maximum yield stress. This is due to its very rough surface morphology limiting the extent of intermolecular hydrogen bonding between adsorbed phosphate layers. Unlike phosphate, pyrophosphate reduces the maximum yield stress of AKP30 α‐Al₂O₃. This is due to the presence of intramolecular hydrogen bonding, thereby impeding effective bridging. A similar result is observed with citrate. The adsorbed pyrophosphate acts as an effective steric barrier keeping interacting particles further apart, thereby weakening the van de Waals attraction. These dispersions with the presence of non‐DLVO forces, that is bridging and steric, did not affect the linear relationship between yield stress and the square of the zeta potential as predicted by the yield stress–DLVO force model. However the relative importance of these non‐DLVO forces affect the value of the critical zeta potential at the point of transition from flocculated to dispersed state. © 2011 Canadian Society for Chemical Engineering     

Theoretical analysis of colloidal interaction energy in nanoparticle suspensions

This study is focused on understanding interaction energies for Al₂O₃ nanoparticle suspensions at high solids loadings. Among the four interaction energies: van der Waals interaction energy, electrostatic interaction energy, steric interaction energy, and depletion interaction energy, the study found that the van der Waals attraction is the dominant mechanism in destabilizing the dispersion system; the steric repulsion is a more effective stabilization mechanism than the electrostatic repulsion. The fundamental cause for an unstable suspension due to the particle–particle close contact and thus attraction at high solids loading can be overcome by increasing the particle–particle repulsion. When a dispersant is used in a suspension, the polymer chain length must be carefully selected so that the dispersant provides enough stabilization but does not compromise the maximum achievable solids loading. If an appropriate dispersant is chosen, up to 45 vol% solids loading suspension can be obtained for the Al₂O₃ nanoparticles.     

Efficient Gene Transfection into Mammalian Cells Mediated by Cross-linked Polyethylenimine

25 kDa branched polyethylenimine (PEI) has successfully been used for in vitro and in vivo gene delivery approaches, but it is cytotoxic. Smaller PEIs are usually non-cytotoxic but less efficient. In order to enhance the gene delivery efficiency and minimize cytotoxicity of PEI, we explored to synthesize cross-linked PEIs with degradable bonds by reacting amines of small branched 2000 Da PEI with small diacrylate (1,4-butanediol diacrylate or ethyleneglycol dimethacrylate) for 2–6 hours. The efficiency of the cross-linked PEIs during in vitro delivering plasmid containing enhanced green fluorescent protein (EGFP) gene reporter and their cytotoxicity were assessed in melanoma B16F10 cell and other cell lines. In vivo gene delivery efficiency was evaluated by direct injection delivery of the EGFP plasmid/cross-linked PEI complexes into mice and by estimating the EGFP expression in animal muscles. Compared to commercially available 25-kDa branched PEI, the cross-linked PEIs reported here could mediate more efficient expression of reporter gene than the 25-kDa PEI control, 19-fold more efficiently in B16F10 cells, 17-fold in 293T cells, 2.3-fold in 3T3 cells, and they exhibited essentially nontoxic at their optimized condition for gene delivery. Furthermore the transfection activity of polyplexs was preserved in the presence of serum proteins. The muscle transfected with the cross-linked PEI prepared here exhibited normal morphology and excellent gene expression. The cross-linked PEIs reported here were evidently more efficient than the commercial 25-kD PEI control and had less cytotoxicity in gene delivery in vitro and in vivo.     

Yield stress-zeta potential relationship of oxide dispersions with adsorbed polyacrylate — Steric effect and zeta potential at the flocculated-dispersed transition state

The yield stress-DLVO force relationship is obeyed by α-Al₂O₃ and alumina-coated TiO₂ dispersions with adsorbed polyacrylate only if the yield stress and its corresponding zeta potential data were collected in the positively charged region. In this region, the underlying surface positive charge density of the particles exceeds the negative charge density of the polyacrylate. At this state the adsorbed polyelectrolyte lies flat on the particle surface forming a steric layer of fixed thickness at a given polymer concentration. In the negative charge region, the steric layer thickness is not constant and hence yield stress-DLVO relationship is not obeyed. The (critical) zeta potential at the flocculated-dispersed transition state decreases with increasing polymer concentration. This result reflects a decreasing van der Waals force as the steric layer increases in thickness. A steric layer ensured that the surface or zeta potential is sufficiently low in the flocculated regime for the DLVO theory to remain valid. The ratio of the critical zeta potential square between alumina-coated TiO₂ and α-Al₂O₃ is an indication of their Hamaker constants ratio in water. The effect of alumina coating on the value of this ratio is presented and discussed.     

Fabrication of transparent yttria ceramics by alcoholic slip-casting

Y₂O₃ transparent ceramics were prepared from alcoholic slurries of Y₂O₃ nanopowders via a slip-casting method to avoid the hydrolysis issue. Polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG) and polyethylenimine (PEI) were used as dispersants to improve the rheological properties of the slurries. It was found that PEI is the most effective dispersant in ethanol. The adsorbed amount of PEI was evaluated by infrared absorption and rheology measurements. Y₂O₃ slurry with a solid loading of 20.8 vol% and a viscosity of <0.1 Pa s at the shear rate of 10 s⁻¹ was obtained using 1.5 wt% PEI. The slurry yielded a homogeneous green body, and finally resulted in a high-quality Y₂O₃ ceramic with the in-line transmittance of 80% at 800 nm.     

Effect of Polyacrylic Acid Addition on Rheology of SiC‐Al2O3‐ZrO2(3Y) Mixed Suspensions

A suspension with good rheology and high stability is crucial for slip casting and gelcasting technology. However, a mixed suspension from two or more different powders usually has bad rheology because of the easy agglomeration of mixed powders caused by the attractive force between the powders with heterocharges. We studied the surface modification of the each single‐component powders (SiC, Al₂O₃, ZrO₂(3Y) powders) and the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders to increase the repulsive force by adjusting the pH value and adding polyacrylic acid (PAA) as dispersant. The PAA addition effects on the SiC‐Al₂O₃‐ZrO₂(3Y) mixture were investigated in terms of zeta potential, pH range for heterocharge region, dispersion of the mixed powders and rheology of the mixed slurry based on the study of each unary suspensions. The results show that before surface modification the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders were agglomerated severely because they were in the heterocharge region with a broad pH range from 3.5 to 8.25, while after surface modification (pH = 10.5, PAA = 0.8wt%) the heterocharge region was narrowed with a relatively narrower pH range from 2.6 to 3.7. The mixed powders with homocharges were dispersed well because of the great electrostatic repulsive force and steric hindrance offered by PAA and the mixed suspensions had favorable rheology.     

Effect of the addition of silica sol on layered extrusion forming of Al2O3-based cores

Layered extrusion forming of ceramic cores with a nanoceramic suspension as a binder was conducted to explore a novel method to produce complex-shaped ceramic cores. Green bodies were prepared using Al₂O₃ particles as precursor materials and silica sol combined with aqueous polyvinyl alcohol solution as a binder. Increasing the silica sol content increased the viscosity of the slurry, enhanced the green bending strength, and decreased the green linear shrinkage. The green microstructure showed the nanosized silica particles were deposited on the surface of the Al₂O₃ particles and among the pores formed by Al₂O₃ particles irregular packing. In addition, increasing the silica sol content increased the bending strength, however, decreased linear shrinkage and open porosity of the sintered bodies. During sintering, the nanosized silica particles converted to the melting phase and reacted with Al₂O₃ and the microstructure of sintered bodies indicated the existence of sintering neck with silica sol addition.     

Rheological behavior of carbon nanotube-alumina nanoparticle dispersion systems

In this work, Al₂O₃ nanoparticle and CNT-Al₂O₃ nanoparticle suspensions were studied. Both Al₂O₃ nanoparticle and CNT-Al₂O₃ nanoparticle systems exhibit shear-thinning behavior. The viscosities increase monotonically with the suspension solids loading. For the 40 vol.% solids loading suspension, CNT effect on the viscosity is not substantial until the content is ≥ 1.3 vol.%. The suspension yield stress to flow provides a measure of the particle-particle networking in the suspension. With the adsorbed poly(acrylic acid) (PAA) layer on the particle surface, substantial colloidal interactions are observed when the solids loading is > 35 vol.% and the CNT content is > 1.3 vol.%. Storage modulus and loss modulus can be used to understand the relative magnitude of the viscoplastic behavior and the elastic behavior of the suspension as well as the transition between the two. The relative magnitude of the dynamic modulii is a strong function of the solids loading and the CNT content.     

Alumina/MWCNTs composites by aqueous slip casting and pressureless sintering

Slip casting of stabilized aqueous suspensions followed by pressureless sintering was used for preparation of dense Al₂O₃/MWCNTs composites. The suspensions were stabilized by commercial polyelectrolyte dispersant Darvan C–N. In order to increase the stability, the pH value of the suspension was adjusted to ∼10. At this pH the highest ζ-potential values of the alumina powder and of the MWCNTs functionalised in boiling nitric acid were achieved. Two different agents, namely ammonium hydroxide and sodium hydroxide, were used for the pH adjustment. Their influence on the viscosity of suspensions and on consolidation and densification behaviour of the Al₂O₃/MWCNT composites was evaluated. The effect of ammonium hydroxide was more pronounced, as confirmed by lower viscosity of the suspension, higher sintered density, and fine-grained microstructure of the sintered composites. The Al₂O₃/t-MWCNTs composites with 0.1 wt% of the MWCNTs, with 99.9% relative density, the mean size of alumina grains ∼1 μm, and homogeneously distributed carbon nanotubes were prepared by the pressureless sintering at 1500 °C.     

Branching and molecular weight distribution of polyethylene SRM 1476

A method of determining the distribution of branching in a polymer is developed employing limiting viscosity numbers (intrinsic viscosity), gel permeation chromatography (GPC), and absolute molecular weight determinations of fractions of the whole polymer. A molecular weight calibration of the GPC column set is first determined empolying these fractions. From the limiting viscosity number measurements of these fractions and their molecular weight distribution determined from the GPC chromatogram, the viscosity–molecular weight relationship is determined by a nonlinear least-squares fitting procedure. For the same molecular weight, the limiting viscosity number of the branched polymer is less than the limiting viscosity number of the linear polymer. From the ratio of the two, the number of branches per unit molecular weight of the branched polymer is calculated. The method was applied to SRM 1476, the standard reference branched polyethylene issued by the National Bureau of Standards. The branching density for the constituents of SRM 1476 rise from zero at molecular weights less than 10,000 to about 6 to 8×10^?5 at molecular weights of 50,000 and above. The branching of SRM 1476 was also determined by the method of Drott and Mendelson, giving a result in fair agreement with the above method.     

Macroporous bead modification with polyethylenimines of different molecular weights as polycationic ligands

Polyethylenimines (PEIs) with different molecular weights [number‐average molecular weights (M_n′s) = 60,000, 1200, and 423] were coupled onto macroporous beads. These rigid and spherical beads were prepared by the crosslinking of 2‐hydroxyethyl methacrylate and ethylene glycol dimethacrylate. The PEI attachment was carried out through epoxy groups yielded in a previous activation step with epichlorohydrin on matrix hydroxyl groups. Different initial concentrations of PEI were assayed. The supports so obtained were characterized by several techniques (Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mercury intrusion porosimetry). All of the PEI‐containing beads were used to analyze the influence that the molecular weight, the shape of the polycationic ligand (PEI), and the degree of coupling onto the matrices may have had on the efficiency of the retention of the bovine serum albumin protein used as a model biomolecule. In these assays, the PEI‐modified beads with M_n = 60,000 showed better results than those modified with PEIs with M_n's of 1200 and 423. The presence of sparse and long chains of PEI 60,000 onto the matrix, by reason of their highest accessibility toward the large protein, may have resulted in a better disposition of functional groups, whereas more short chains in the other PEIs (M_n's = 1200 and 423) used as ligands would not have. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of surfactant addition sequence on the suspension properties and electrophoretic deposition behaviour of alumina and zirconia

A well-known polyelectrolyte salt, ammonium polymethacrylate (Darvan-C) is used to stabilise ethanol-based Al₂O₃ and Ce-ZrO₂ suspensions with butylamine addition. The sequence in which n-butylamine and Darvan-C are added to the suspension greatly affects the properties of the wet deposit obtained by electrophoretic deposition. To investigate this effect, electrical conductivity of the suspension and the shear rate dependence of its viscosity are investigated. When n-butylamine is added first, the equilibrium in the suspension is almost immediately reached and a plastically deformable wet deposit is obtained over a large n-butylamine/Darvan-C ratio. The suspension has a shear-thinning viscosity and the deformable deposit is characterised by a high solvent content, which allows the rearrangement of particles during drying. When Darvan-C is added before the n-butylamine, the wet deposit is smooth and rigid. The suspension has a lower viscosity and a near-Newtonian behaviour is observed. A similar behaviour is observed for Al₂O₃ and Ce-ZrO₂ suspensions. The green density of the dried deposits is not influenced by the addition sequence and higher green densities are obtained for Al₂O₃ when compared to Ce-ZrO₂.     

Carbon Membranes Prepared from a Polymer Blend of Polyethylene Glycol and Polyetherimide

Through a dip‐coating technique, carbon membranes were produced from a polymer blend consisting of the thermally stable polymer polyetherimide (PEI) and the thermally labile polymer polyethylene glycol (PEG). The PEG/PEI carbon membranes were synthesized on an alumina support coated with an Al₂O₃ intermediate layer. The polymer blend ratio and carbonization temperature influenced the structure and permeation performance of the derived carbon membranes. The porosity of the PEG/PEI carbon membranes increased with higher PEG content in the blends. However, the derived carbon membranes tended to lose gas permeability with raising the carbonization temperatures. The carbon membranes were successfully optimized in order to achieve the highest CO₂/CH₄ and CO₂/N₂ selectivities.