Comparative electron microscopy particle sizing of TiO2 pigments: sample preparation and measurement.

Titanium dioxide (TiO2) pigment is a non-toxic, particulate material in widespread use and found in everyone's daily life. The particle size of the anatase or rutile crystals are optimised to produce a pigment that provides the best possible whiteness and opacity. The average particle size is intentionally much larger than the 100 nm boundary of the EU nanomaterial definition, but the TiO2 pigment manufacturing processes results in a finite nanoscale content fraction. This optically inefficient nanoscale fraction needs to be quantified in line with EU regulations. In this paper, we describe the measurement procedures used for product quality assurance by three TiO2 manufacturing companies and present number-based primary particle size distributions (PSDs) obtained in a round-robin study performed on five anatase pigments fabricated by means of sulfate processes in different plants and commonly used worldwide in food, feed, pharmaceutical and cosmetic applications. The PSDs measured by the three titanium dioxide manufacturers based on electron micrographs are in excellent agreement with one another but differ significantly from those published elsewhere. Importantly, in some cases, the PSDs result in a different regulatory classification for some of the samples tested. The electron microscopy results published here are supported by results from other complementary methods including surface area measurements. It is the intention of this publication to contribute to an ongoing discussion on size measurements of TiO2 pigments and other particulate materials and advance the development of widely acceptable, precise, and reproducible measurement protocols for measuring the number-based PSDs of particulate products in the size range of TiO2 pigments.

Particle Size Distributions for Cellulose Nanocrystals Measured by Transmission Electron Microscopy: An Interlaboratory Comparison.

Particle size is a key parameter that must be measured to ensure reproducible production of cellulose nanocrystals (CNCs) and to achieve reliable performance metrics for specific CNC applications. Nevertheless, size measurements for CNCs are challenging due to their broad size distribution, irregular rod-shaped particles, and propensity to aggregate and agglomerate. We report an interlaboratory comparison (ILC) that tests transmission electron microscopy (TEM) protocols for image acquisition and analysis. Samples of CNCs were prepared on TEM grids in a single laboratory, and detailed data acquisition and analysis protocols were provided to participants. CNCs were imaged and the size of individual particles was analyzed in 10 participating laboratories that represent a cross section of academic, industrial, and government laboratories with varying levels of experience with imaging CNCs. The data for each laboratory were fit to a skew normal distribution that accommodates the variability in central location and distribution width and asymmetries for the various datasets. Consensus values were obtained by modeling the variation between laboratories using a skew normal distribution. This approach gave consensus distributions with values for mean, standard deviation, and shape factor of 95.8, 38.2, and 6.3 nm for length and 7.7, 2.2, and 2.9 nm for width, respectively. Comparison of the degree of overlap between distributions for individual laboratories indicates that differences in imaging resolution contribute to the variation in measured widths. We conclude that the selection of individual CNCs for analysis and the variability in CNC agglomeration and staining are the main factors that lead to variations in measured length and width between laboratories.

Metal-semiconductor pair nanoparticles by a physical route based on bipolar mixing.

In this report a methodology is described and demonstrated for preparing Au-Ge pair nanoparticles with known compositions by extending and modifying the basic steps normally used to synthesize nanoparticles in carrier gas. For the formation of pair nanoparticles by bipolar mixing, two oppositely charged aerosols of nanoparticles having the desired size are produced with the help of two differential mobility analyzers. Then both are allowed to pass through a tube, which provides sufficient residence time to result in nanoparticle pair formation due to Brownian collisions influenced by Coulomb forces. The effect of residence time on the formation of nanoparticle pairs as well as the influence of diffusion and discharging is described. Subsequently, necessary modifications to the experimental setup are demonstrated systematically. The kinetics of nanoparticles pair formation in a carrier gas is also calculated and compared with measurements made with the help of an online aerosol size analysis technique. This synthesis of nanoparticle pairs can be seen as a possible route towards Janus-type nanoparticles.

A reproducible number-based sizing method for pigment-grade titanium dioxide.

A strong demand for reliable characterization methods of particulate materials is triggered by the prospect of forthcoming national and international regulations concerning the classification of nanomaterials. Scientific efforts towards standardized number-based sizing methods have so far been concentrated on model systems, such as spherical gold or silica nanoparticles. However, for industrial particulate materials, which are typically targets of regulatory efforts, characterisation is in most cases complicated by irregular particle shapes, broad size distributions and a strong tendency to agglomeration. Reliable sizing methods that overcome these obstacles, and are practical for industrial use, are still lacking. By using the example of titanium dioxide, this paper shows that both necessities are well met by the sophisticated counting algorithm presented here, which is based on the imaging of polished sections of embedded particles and subsequent automated image analysis. The data presented demonstrate that the typical difficulties of sizing processes are overcome by the proposed method of sample preparation and image analysis. In other words, a robust, reproducible and statistically reliable method is presented, which leads to a number-based size distribution of pigment-grade titanium dioxide, for example, and therefore allows reliable classification of this material according to forthcoming regulations.

Paired twins and [112] morphology in GaP nanowires.

Formation of random as well as periodic planar defects can occur during vapor-liquid-solid growth of nanowires with the zinc-blende crystal structure. Here we investigate the formation of pairs of twin planes in GaP nanowires. In such pairs, the first twin plane is formed at a random position, rapidly followed by the formation of a second twin plane of which the position is directly related to that of the first one. We show that the triangular [112] morphology of the nanowire is a key element in the formation of these twin pairs. We have extended our previous kinetic nucleation model and show that this describes the development of the nanowire morphology and its relation with the formation of single and paired twin planes.

Subsurface changes of a MoM hip implant below different contact zones.

Metal-on-metal hip arthroplasties undergo distinct release of toxic metal particles and ions. Thus, it is necessary to minimize this. In order to evaluate the wear behaviour of metal-on-metal hip replacements it is essential to understand the micro-structural changes in the sub-surface region. Previous studies revealed that cobalt chromium metal-on-metal implants are able to alter their mechanical behaviour by adjusting the microstructure to load. The reason for this is the so-called mechanical mixing. This means that a nano-crystal layer is formed by rotating clusters of atoms that incorporate denatured proteins from the interfacial medium. This is followed by a layer of rhombic shaped nano-crystals in between sheared epsilon-martensite lathes, twins, and stacking faults. Although the primary wear zone has been well characterized, the sub-surface structure of the stripe wear and the non-contact zone of the hip ball have yet to be analysed. For this study a 28-mm cobalt base alloy femoral head and acetabular cup were analysed. The implant was simulator tested for 5 million cycles with the application of micro-separation resulting in a clearly visible stripe wear appearance. The TEM micrograph of the primary wear zone of the ball confirmed the presence of a sub-surface layer of nano-crystals. The thickness of this layer was approximately 200 nm and the average grain diameter ranged from 35 to 40 nm. Within the stripe wear zone the micrographs also revealed a nano-crystal layer but with a thickness of only 50 nm and an average grain diameter from 15 to 20 nm. The carbon and oxygen content was highest closest to the surface which proves the occurrence of mechanical mixing. The non-contact zone of the ball was analysed as well. When compared to the primary wear zone a nano-crystal layer with similar thickness but with an average grain diameter smaller than 15 nm was observed.

"Work-Hardenable" ductile bulk metallic glass.

Usually, monolithic bulk metallic glasses undergo inhomogeneous plastic deformation and exhibit poor ductility (< 1%) at room temperature. We present a new class of bulk metallic glass, which exhibits high strength of up to 2265 MPa together with extensive "work hardening" and large ductility of 18%. Significant increase in the flow stress was observed during deformation. The "work-hardening" capability and ductility of this class of metallic glass is attributed to a unique structure correlated with atomic-scale inhomogeneity, leading to an inherent capability of extensive shear band formation, interactions, and multiplication of shear bands.

Characterization of individual aerosol particles in workroom air of aluminium smelter potrooms.

Aerosol particles with aerodynamic diameters between 0.18 and 10 microm were collected in the workroom air of two aluminium smelter potrooms with different production processes (Soderberg and Prebake processes). Size, morphology and chemical composition of more than 2000 individual particles were determined by high resolution scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on chemical composition and morphology, particles were classified into different groups. Particle groups with a relative abundance above 1%(by number) include aluminium oxides, cryolite, aluminium oxides-cryolite mixtures, soot, silicates and sea salt. In both production halls, mixtures of aluminium oxides and cryolite are the dominant particle group. Many particles have fluoride-containing surface coatings or show agglomerations of nanometer-sized fluoride-containing particles on their surface. The phase composition of approximately 100 particles was studied by transmission electron microscopy. According to selected area electron diffraction, sodium beta-alumina (NaAl(11)O(17)) is the dominant aluminium oxide and cryolite (Na(3)AlF(6)) the only sodium aluminium fluoride present. Implications of our findings for assessment of adverse health effects are discussed.