The thermal conductivity, k, of nanoscale colloidal suspensions (also known as nanofluid), consisting of nanoparticles suspended in a base liquid, is much higher than the thermal conductivity of the base liquid at very small volume fractions of the nanoparticles. However, experimental results from various groups all across the world have shown various anomalies such as a peak in the enhancement of k with respect to nanoparticle size, an increase as well as a decrease in the ratio of k of these colloidal solutions with the k of the base fluid with increasing temperature, and a dependence of k on pH and time. In this paper, the aggregation kinetics of nanoscale colloidal solutions are combined with the physics of thermal transport to capture the effects of aggregation on k. Results show that the observed anomalies reported in experimental work can be well described by taking aggregation kinetics into account. Finally, we show that colloidal chemistry plays a significant role in deciding the k of colloidal nanosuspensions.

Effect of aggregation kinetics on the thermal conductivity of nanoscale colloidal solutions (nanofluid)

A review of floc strength and breakage.

This work aims at a more fundamental understanding of the rheological behaviour of nanofluids and the interpretation of the discrepancy in the recent literature. Both experiments and theoretical analyses are carried out with the experimental work on ethylene glycol (EG)-based nanofluids containing 0.5–8.0 wt% spherical TiO2 nanoparticles at 20–60 °C and the theoretical analyses on the high shear viscosity, shear thinning behaviour and temperature dependence. The experimental results show that the EG-based nanofluids are Newtonian under the conditions of this work with the shear viscosity as a strong function of temperature and particle concentration. The relative viscosity of the nanofluids is, however, independent of temperature. The theoretical analyses show that the high shear viscosity of nanofluids can be predicted by the Krieger–Dougherty equation if the effective nanoparticle concentration is used. For spherical nanoparticles, an aggregate size of approximately 3 times the primary nanoparticle size gives the best prediction of experimental data of both this work and those from the literature. The shear thinning behaviour of nanofluids depends on the effective particle concentration, the range of shear rate and viscosity of the base liquid. Such non-Newtonian behaviour can be characterized by a characteristic shear rate, which decreases with increasing volume fraction, increasing base liquid viscosity, or increasing aggregate size. These findings explain the reported controversy of the rheological behaviour of nanofluids in the literature. At temperatures not very far from the ambient temperature, the relative high shear viscosity is independent of temperature due to negligible Brownian diffusion in comparison to convection in high shear flows, in agreement with the experimental results. However, the characteristic shear rate can have strong temperature dependence, thus affecting the shear thinning behaviour. The theoretical analyses also lead to a classification of nanofluids into dilute, semi-dilute, semi-concentrated and concentrated nanofluids depending on particle concentration and particle structuring.

https://iopscience.iop.org/article/10.1088/1367-2630/9/10/367/pdf

Rheological behaviour of nanofluids

The growth, breakage, regrowth, and fractal nature of flocs was investigated by use of a laser diffraction particle sizing device. A range of coagulants were investigated for the coagulation of natural organic matter (NOM) and compared to other coagulated systems. The results showed NOM floc structural characteristics varied in steady-state size depending upon which coagulant was used. When compared to other systems, the order of floc size was Fe precipitate > Fe-NOM > latex (in NaCl solution). Floc regrowth after exposure to high shear was limited for all of the flocs under investigation other than for latex in an inert electrolyte. This highlighted differences in the internal bonding structure of flocs, with the results suggesting that physical bonds have a capacity to re-form after breakage. Fractal dimension analysis by small-angle laser light scattering (SALLS) had limited applicability to large flocs that dominated all of the systems under investigation, but the degree of compaction increased as flocs were broken in high shear. This provided a possible mechanistic reason for the irreversible breakage seen.

Breakage, regrowth, and fractal nature of natural organic matter flocs.

Effect of aggregation on the viscosity of copper oxide–gear oil nanofluids

Suspensions of a variety of different aluminum oxides have previously been shown to require very high concentrations of chloride and nitrate anions (>0.5 M) to induce rapid aggregation. This high stability has been accredited to the presence of surface forces considered to be due to the formation of highly charged Al13 polymeric species at slightly acidic pH's and aluminum oxyhydroxide gel formation under alkaline conditions. The effect of this stability on the structure of the resulting aggregates is investigated here using well-established static light-scattering techniques. Power law behavior of scattered light intensity as a function of scattering wave vector is observed in all cases and is suggestive of fractal structure. The fractal dimensions obtained fall within the expected range of 1.8 to 2.3 observed for colloidal aggregates but do not appear to follow the typical observations for colloids destabilized by indifferent electrolytes where lower fractal dimensions are associated with rapid (diffusion-limited) aggregation and higher fractal dimensions with slower (reaction-limited) aggregation. Indeed, relatively constant fractal dimensions (2.10 to 2.25) are observed over the range of salt concentrations at which the slow to rapid aggregation rate transformation occurs with, if anything, a slightly higher fractal dimension observed for higher aggregation rates. The presence of specifically binding sulfate anions appears to negate the strong near-distance repulsive forces leading to rapid aggregation at low (1 to 2 mM) sulfate concentrations. Significantly lower fractal dimensions (1.85 to 1.91) are observed for aggregates formed by destabilization using sulfate ions than obtained when chloride or nitrate are used with, again, an apparent slight increase in fractal dimension upon increasing aggregation rate.

http://slapper.apam.columbia.edu/bib/papers/waite_jcis01.pdf

J.K. Cleaver

Papers

Aggregation Kinetics and Fractal Structure of γ-Alumina Assemblages