Viscosity of aqueous and cyanate ester suspensions containing alumina nanoparticles

Abstract

The viscosities of both aqueous and cyanate ester monomer (BECy) based suspensions of alumina nanoparticle were studied. The applications for these suspensions are different: aqueous suspensions of alumina nanoparticles are used in the production of technical ceramics made by slip casting or tape casting, and the BECy based suspensions are being developed for use in an injection-type composite repair resin. In the case of aqueous suspensions, it is advantageous to achieve a high solids content with low viscosity in order to produce a high quality product. The addition of a dispersant is useful so that higher solids content suspensions can be used with lower viscosities. For BECy suspensions, the addition of nanoparticles to the BECy resin is expected to enhance the mechanical properties of the cured composite. The addition of saccharides to aqueous suspensions leads to viscosity reduction. Through DSC measurements it was found that the saccharide molecules formed a solution with water and this resulted in lowering the melting temperature of the free water according to classic freezing point depression. Saccharides also lowered the melting temperature of the bound water, but this followed a different rule. The shear thinning and melting behaviors of the suspensions were used to develop a model based on fractal-type agglomeration. It is believed that the structure of the particle flocs in these suspensions changes with the addition of saccharides which leads to the resultant viscosity decrease. The viscosity of the BECy suspensions increased with solids content, and the viscosity increase was greater than predicted by the classical Einstein equation for dilute suspensions. Instead, the Mooney equation fits the viscosity behavior well from 0-20 vol% solids. The viscosity reduction achieved at high particle loadings by the addition of benzoic acid was also investigated by NMR. It appears that the benzoic acid interacts with the surface of the alumina particle which may be the cause of the viscosity reduction. The flow behavior of alumina particles in water and BECy is markedly different. Aqueous alumina suspensions are shear thinning at all alumina loadings and capable of 50 vol% loading before losing fluidity whereas BECy/alumina suspensions show Newtonian behavior up to 5 vol%, and above 5 vol% show shear thinning at all shear rates. Highly loaded suspensions (i.e. 20vol% alumina) exhibit shear thinning at low and moderate shear rates and shear thickening at higher shear rates. The maximum particle loading for a fluid suspension, in this case, appears to be about 20 vol%. The difference in the viscosity of these suspensions must be related to the solvent-particle interactions for each system. The reason is not exactly known, but there are some notable differences between BECy and water. Water molecules are {approx}0.28 nm in length and highly hydrogen bonded with a low viscosity (1 mPa's) whereas in the cyanate ester (BECy) system, the solvent molecule is about 1.2 nm, in the largest dimension, with surfaces of varied charge distribution throughout the molecule. The viscosity of the monomer is also reasonably low for organic polymer precursor, about 7 mPa's. Nanoparticles in water tend to agglomerate and form flocs which are broken with the shear force applied during viscosity measurement. The particle-particle interaction is very important in this system. In BECy, the particles appear to be well dispersed and not as interactive. The solvent-particle interaction appears to be most important. It is not known exactly how the alumina particles interact with the monomer, but NMR suggests hydrogen bonding. These hydrogen bonds between the particle and monomer could very well affect the viscosity. A conclusion that can be reached in this work is that the presence of hydroxyl groups on the surface of the alumina particles is significant and seems to affect the interactions between other particles and the solvent. Thus, the hydrogen bonding between particles, particle/additive and/or particle/solvent dictates the behavior of nanosized alumina particle suspensions. The addition of dispersants can change the particle interactions and hence reduce the suspension viscosity. This was demonstrated with saccharides in the aqueous system and with benzoic acid in suspensions with BECy.