Lilian de Martín

The role of the hydrogen bond in dense nanoparticle–gas suspensions

The effect of surface characteristics on the interaction between nanoparticles and their agglomeration in dense gas suspensions is still not fully understood. It is known that when the surface is covered with hydroxyl groups, the interaction between nanoparticles becomes substantially stronger than in the absence of these groups; this strengthening is typically attributed to the formation of capillary bridges between the particles. However, this work shows that part of the increase of the interaction is due to the direct hydrogen bonds formed between the surfaces of the polar particles. Dry nitrogen was used to fluidize polar (hydrophilic) and apolar (hydrophobic) SiO2, TiO2 and Al2O3 particles, with a size ranging from 13 to 21 nm. The dry polar particles showed smaller bed expansion and larger minimum fluidization velocity compared to their apolar counterparts, indicating stronger interparticle forces. The results show the importance of including the formation of hydrogen bonds in the modeling of the interaction between dry and polar nanoparticles.

Multidimensional Nature of Fluidized Nanoparticle Agglomerates

We show that fluidized nanoparticle agglomerates are hierarchical fractal structures with three fractal dimensions: one characterizing sintered aggregates formed during nanoparticle synthesis, one that is also found in stored agglomerates and represents unbroken agglomerates, and one describing the large agglomerates broken during fluidization. This has been possible by using spin-echo small-angle neutron scattering-a relatively novel technique that, for the first time, allowed to characterize in situ the structure of fluidized nanoparticle agglomerates from 21 nm to ∼20 μm. The results show that serial agglomeration mechanisms in the gas phase can generate nanoparticle clusters with different fractal dimensions, contradicting the common approach that considers fluidized nanoparticle agglomerates as single fractals, in analogy to the agglomerates formed by micron-sized particles. This work has important implications for the fluidization field but also has a wider impact. Current studies deal with the formation and properties of clusters where the building blocks are particles and the structure can be characterized by only one fractal dimension. However, fluidized nanoparticle agglomerates are low-dimensional clusters formed by higher-dimensional clusters that are formed by low-dimensional clusters. This multifractality demands a new type of multiscale model able to capture the interplay between different scales.

A model to estimate the size of nanoparticle agglomerates in gas−solid fluidized beds

The estimation of nanoparticle agglomerates’ size in fluidized beds remains an open challenge, mainly due to the difficulty of characterizing the inter-agglomerate van der Waals force. The current approach is to describe micron-sized nanoparticle agglomerates as micron-sized particles with 0.1–0.2-μm asperities. This simplification does not capture the influence of the particle size on the van der Waals attraction between agglomerates. In this paper, we propose a new description where the agglomerates are micron-sized particles with nanoparticles on the surface, acting as asperities. As opposed to previous models, here the van der Waals force between agglomerates decreases with an increase in the particle size. We have also included an additional force due to the hydrogen bond formation between the surfaces of hydrophilic and dry nanoparticles. The average size of the fluidized agglomerates has been estimated equating the attractive force obtained from this method to the weight of the individual agglomerates. The results have been compared to 54 experimental values, most of them collected from the literature. Our model approximates without a systematic error the size of most of the nanopowders, both in conventional and centrifugal fluidized beds, outperforming current models. Although simple, the model is able to capture the influence of the nanoparticle size, particle density, and Hamaker coefficient on the inter-agglomerate forces.

Multidimensionality in Fluidized Nanopowder Agglomerates

recent years, the interest in fluidization as a mean to process nanoparticles is strongly increasing. Due to the small size of the nanoparticles, which makes van der Waals forces predominate, they do not fluidize as single particles but as agglomerates. Various researchers using settling experiments and bed expansion measurements conclude that fluidized agglomerates are fractal structures with a single fractal dimension of 2.5. Based on microscopy results, Wang et al. “Powder Technology 124, 152–C159 (2002)” propose a hierarchical structure, which seems in contradiction with the use of only one fractal dimension as a descriptor of the whole structure. Moreover, it is not clear whether the structure presented by the agglomerates ex-situ is the same during fluidization. Hence, in this work we have characterized in-situ the internal structure of fluidized agglomerates by means of spin-echo small-angle neutron scattering (SESANS). We show that the structure of the agglomerates present at least two fractal dimensions. One of them is ? 2.1 and characterizes the primary strong agglomerates. The second one is ? 2.8 and characterizes the larger agglomerates formed by the primary agglomerates.

Optimizing off-lattice Diffusion-Limited Aggregation

Abstract We present a technique to improve the time scaling of Diffusion-Limited Aggregation simulations. The proposed method reduces the number of calculations by making an extensive use of the RAM memory to store information about the particles’ positions and distances. We have simulated clusters up to 5 ⋅ 10 6 particles in 2D and up to 1 ⋅ 10 6 particles in 3D and compared the calculation times with previous algorithms proposed in the literature. Our method scales t ∝ N p 1.08 , outperforming the current optimization techniques.