Inorganic Particle Size Measurement Below 100 nm - Where Life Gets Difficult
Several different methods, photon correlation spectroscopy (PCS), an X-ray disc centrifuge (XDC), X-ray powder diffraction (XRD) and high resolution scanning and transmission electron microscopy combined with image analysis have been used to characterise the particle size distributions of several inorganic powders ( Al2O3, FexOy, SiO2). The different powders cover the size range from 5 nm to around 100nm and have different shapes and degrees of agglomeration. The gamma alumina is highly agglomerated, the silicas are roughly spherical and the iron oxide slightly elongated but well dispersed (low agglomeration). The state of agglomeration and how different treatments such as milling and surface modification affect the state of agglomeration is often poorly described in most nanoparticle studies. We shall illustrate how agglomeration can described for an “as received” and attrition milled gamma alumina, both as a function of milling time and bead size. Results are presented after consideration of the hydrodynamic density in the sedimentation methods, and light scattering for the optical based methods. The results with model spherical silica powders (Dv50 of 12, 35 and 80 nm) show how the accuracy of the sedimentation methods depends strongly on a knowledge of the particle hydrodynamic density. This can be affected greatly by particle or agglomerate porosity, the thickness of the electrical double layer or strongly bound hydration layer often found for nanoparticles in the aqueous dispersions investigated. Precipitated iron oxide particles with sizes around 10 nm start pushing the limits of several of the methods. A careful protocol had to be developed using XRD and TEM to allow quick and reliable measurements to be made using PCS. This allowed the investigation of the effect of PVA adsorption on the size of the iron oxides important for biomedical applications.
Dispersion and Grinding of Oxide Powders into an Aqueous Slurry
The present paper deals with a comprehensive analysis of the dispersion behavior of oxide powders to determine accurate conditions for mixing and grinding dense slurries without the use of steric dispersing agents. The experimental support of the work was the synthesis of (Zr,Sn)TiO4 microwave dielectric ceramics by the solid-state reaction of raw materials mixed and ground by attrition milling. Zeta potential measurements were performed on the raw materials versus pH to determine the optimum pH of the slurry, allowing a good dispersion of all the species: the absolute value of the zeta potential of every powder >20 mV, with all potentials having the same sign. During the grinding process, as the surface of the materials increases due to the breakup of the grains, surface reaction occurs with the dispersion liquid, and pH must be continuously adjusted to be maintained at an adequate level. We have correlated these characterizations of the optimal processing conditions with the rheological behavior of the slurries, thus providing an analysis of the flocculated or deflocculated state. When applied to synthesizing (Zr,Sn)TiO4 microwave dielectric ceramics, these conclusions made it possible to produce reproducible resonators with a k= 37 dielectric constant and characterized by a quality factor, Q×F > 60 000 GHz measured at 3 GHz, the highest value reported for this composition.
Particle characterization in centrifugal fields. Comparison between ultracentrifugation and sedimentation field-flow fractionation.
A ten-component mixture of polystyrene latex particles in the 67-1220 nm size range was subjected to analysis by analytical ultracentrifugation (AUC) and sedimentation field-flow fractionation (SdFFF) using programmed and constant fields. The AUC analysis of the mixture yielded diameter values in good agreement with data determined on the separate components; the relative amounts of each component in the mixture were likewise closely reproducing the sample's known composition. Diameters determined by SdFFF, either in a constant- or programmed-field mode, were in good agreement with the AUC for particles smaller than about 500 nm. For the sample's larger components, however, particularly the programmed mode showed diameter values smaller than expected. In addition, field programming resulted in incomplete recoveries of the larger particles, leading to more or less distorted mass distributions for the complex sample. The observed discrepancies, which are thought to result from events at the analytical wall in the FFF channel, suggested a protocol for accurate sizing, as opposed to fingerprinting, of samples with broad size distribution. By tracking sizes and amounts of the different components at different but constant field strengths, and retaining as analytically valid only those data recorded in a retention range from five to about thirty column volumes, it was possible to determine sizes and amounts in good agreement with known parameters for the sample. Unlike the AUC procedure, SdFFF produces fractions of a high degree of uniformity, which lend themselves to a secondary analysis, e.g. by electron microscopy, as shown in the study.