A thermal perspective of flash sintering: The effect of AC current ramp rate on microstructure evolution

In flash sintering experiments, the thermal history of the sample is key to understanding the mechanisms underlying densification rate and final properties. By combining robust temperature measurements with current-ramp-rate control, this study examined the effects of the thermal profile on the flash sintering of yttria-stabilized zirconia, with experiments ranging from a few seconds to several hours. The final density was maximized at slower heating rates, although processes slower than a certain threshold led to grain growth. The amount of grain growth observed was comparable to a similar conventional thermal process. The bulk electrical conductivity correlated with the maximum temperature and cooling rate. The only property that exhibited behavior that could not be attributed to solely the thermal profile was the grain boundary conductivity, which was consistently higher than conventional in flash sintered samples. These results suggest that, during flash sintering, athermal electric field effects are relegated to the grain boundary.     

High-temperature stabilization of polypropylene using hindered phenol–thioester stabilizer combinations,Part 1: Optimization and efficacy via nondust blends

The thermal degradation of unstabilized polypropylene has been investigated under long-term processing (twin extruder) and thermal aging at 150°C, with additive concentration studies on combinations of an established hindered phenolic antioxidant (pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) [S1010] and two popular thioesters (distearyl-3,3′-thiodipropionate [DSTDP] and didodecyl-3,3′-thiodipropionate [DLTDP]) using melt flow rate, carbonyl index and powder diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (FTIR), and differential scanning calorimetry (DSC) (oxidation induction time [OIT]) and ultimate embrittlement time (Fracture) on injection-molded test pieces. It was found that 20:80 phenol:thioester ratios provided the best long-term thermal stability (LTTS); however, this was the reverse for processing stabilization (80:20), underlining the antioxidant nature of the two stabilizers (long term vs. melt). Melt preblending of the stabilizers (to form a no-dust blend) gave rise to improved LTTS. DRIFTS FTIR indicated that there was an improvement in preblending the additives, which removed any volatile impurities. Increased additive dispersion and localized potential efficacy in the stabilization cycle is important, as well as possible improved addition of the additives to the extruder rather than fine powder. The data are discussed in relation to the long-term stabilization of polypropylene in high-temperature applications such as under the bonnet of automobiles where minimizing stabilizer losses and maximizing synergy are important.     

Interlaced layer thicknesses within single laser powder bed fusion geometries

The geometrical design freedoms associated with additive manufacturing techniques are currently well exploited and finding commercial application. The capability of layer-based processes to allow modification of composition and microstructure in process to achieve functional grading is currently a growing topic. In this work, a method is demonstrated for varying layer thickness within single components that allows part sections to be interlaced for the purpose of locally manipulating material and structural properties. Demonstrator geometries are explored here which exhibit the interfaces within specimens constituted of both 30 µm and 150 µm. Accordingly, a new design freedom for laser powder bed fusion is created.     

Occupational exposure and health risks of volatile organic compounds of hotel housekeepers: Field measurements of exposure and health risks

Hotel housekeepers represent a large, low-income, predominantly minority, and high-risk workforce. Little is known about their exposure to chemicals, including volatile organic compounds (VOCs). This study evaluates VOC exposures of housekeepers, sources and factors affecting VOC levels, and provides preliminary estimates of VOC-related health risks. We utilized indoor and personal sampling at two hotels, assessed ventilation, and characterized the VOC composition of cleaning agents. Personal sampling of hotel staff showed a total target VOC concentration of 57 ± 36 µg/m³ (mean ± SD), about twice that of indoor samples. VOCs of greatest health significance included chloroform and formaldehyde. Several workers had exposure to alkanes that could cause non-cancer effects. VOC levels were negatively correlated with estimated air change rates. The composition and concentrations of the tested products and air samples helped identify possible emission sources, which included building sources (for formaldehyde), disinfection by-products in the laundry room, and cleaning products. VOC levels and the derived health risks in this study were at the lower range found in the US buildings. The excess lifetime cancer risk (average of 4.1 × 10⁻⁵) still indicates a need to lower exposure by reducing or removing toxic constituents, especially formaldehyde, or by increasing ventilation rates.     

Applications of analytical electron microscopy to guide the design of boron carbide

Compositional analysis of boron carbide on nanometer length scales to examine or interpret atomic mechanisms, for example, solid-state amorphization or grain-boundary segregation, is challenging. This work reviews advancements in high-resolution microanalysis to characterize multiple generations of boron carbide. First, ζ-factor microanalysis will be introduced as a powerful (scanning) transmission electron microscopy ((S)TEM) analytical framework to accurately characterize boron carbide. Three case studies involving the application of ζ-factor microanalysis will then be presented: (1) accurate stoichiometry determination of B-doped boron carbide using ζ-factor microanalysis and electron energy loss spectroscopy, (2) normalized quantification of silicon grain-boundary segregation in Si-doped boron carbide, and (3) calibration of a scanning electron microscope X-ray energy-dispersive spectroscopy (XEDS) system to measure compositional homogeneity differences of B/Si-doped arc-melted boron carbides in the as-melted and annealed conditions. Overall, the improvement and application of advanced analytical tools have helped better understand processing–microstructure–property relationships and successfully manufacture high-performance ceramics.     

Oxidation‐led decomposition of hexagonal boron nitride coatings on alloy substrates at 900 °C: Ti‐6Al‐4V

Hexagonal boron nitride (h‐BN) coatings on Ti‐6Al‐4V substrates undergo complete decomposition in air at 900 °C. This fate is similar to that of this ceramic material on chromia‐former alloys, and unlike that of a mass of powder treated in isolation. As the ceramic and alloy oxidize concurrently, outwardly diffusing aluminum (III) ions but not the predominant titanium (IV) ions react with the boron trioxide that forms around the h‐BN basal plane peripheries. Resultant aluminum borate is incorporated into the growing scale and the boron trioxide diffusion barrier is depleted. By this mechanism, the oxidation of h‐BN is maintained at an enhanced rate, until both this material and its oxide completely decompose. Liberated nitrogen from the oxidation of h‐BN can enter the underlying scale as a randomly distributed solute in rutile solid solution. The post‐coating oxide‐atmosphere interface comprises elongated aluminum borate crystallites protruding through at the boundaries between 3–5 at% nitrogen‐doped rutile grains. It differs significantly from that of oxidized, uncoated Ti‐6Al‐4V, which is occupied by a thin α‐alumina layer atop rutile. This interface does not change with an additional 72 h of heat‐treatment.     

β-Diketonate versus β-Ketoiminate: The Importance of a Ferrocenyl Moiety in Improving the Anticancer Potency

Herein we present a library of fully characterized β-diketonate and β-ketoiminate compounds that are functionalized with a ferrocenyl moiety. Their cytotoxic potential has been determined by screening against human breast adenocarcinomas (MCF-7 and MDA-MB-231), human colorectal carcinoma p53 wild type (HCT116 p53^+/+) and normal human prostate (PNT2) cell lines. The ferrocenyl β-diketonate compounds are more than 18 times more cytotoxic than the ferrocenyl β-ketoiminate analogues. Against MCF-7, compounds functionalized at the meta position are up to nine times more cytotoxic than when functionalized at the para position. The ferrocenyl β-diketonate compounds have increased selectivity towards MCF-7 and MDA-MB-231, with several complexes having selectivity index (SI) values that are more than nine times (MCF-7) and more than six times (MDA-MB-231) that of carboplatin. The stability of these compounds in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) has been assessed by NMR spectroscopy and mass spectrometry studies, and the compounds show no oxidation of the iron center from Fe^II to Fe^III. Cytotoxicity screening was performed in both DMSO and DMF, with no significant differences observedin their potency.     

Extrusion of highly filled flexible polymer sheet

Highly-filled polymer systems include color masterbatches, feedstocks for powder injection molding, and rigid sheets with high levels of flame retardants, but they have not been explored for flexible sheet. This work investigated the (a) selecting a polymer matrix with enough melt strength and flexibility to form a stable sheet with high filler loading, (b) the maximum achievable filler loading for the sheet, and (c) optimizing the process of extruding a highly-filled flexible polymer system. Extrusion grade low-density polyethylene (LDPE) provided sufficient flexibility and permitted a maximum filler loading of 36 vol% (~78 wt%). Good dispersion of the nanoparticle filler, however, required two passes through multiple screw extruders and a small reduction in the viscosity of the LDPE. Sheet with thickness of 415 μm, surface roughness of <1 μm, and sufficient flexibility was extruded continuously at a rate of 10 m/min., but it required a more traditional coat hanger manifold to prevent filler hang up in the sheet die. The filler particles were distributed uniformly through the core and skin of the sheet, giving the sheet good mechanical properties.