Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends - Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HDPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organomodified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep increasing the organoclay content eventually results in a high degree of PA6 phase continuity. Rheological analyses reveal that the filler loading at which the polyamide assembles in a continuous network corresponds to the critical threshold for its rheological transition from a liquid- to a gel-like behaviour, which is indicative of the structuring of the filler inside the host PA6. On the basis of this finding, a schematic mechanism is proposed in which the role of the filler in driving the space arrangement of the polymer phases is discussed. Finally, we show that the synergism between the reinforcing action of the filler and its ability to affect the blend microstructure can be exploited in order to enhance relevant technological properties of the materials, such as their high temperature structural integrity.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.

Catalytic supercritical water gasification of plastics with supported RuO2:a potential solution to hydrocarbons-water pollution problem

Here we report on a potential catalytic process for efficient clean-up of plastic pollution in waters, such as the Great Pacific Garbage Patch (CPGP). Detailed catalytic mechanisms of RuO2 during supercritical water gasification of common polyolefin plastics including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and polystyrene (PP), have been investigated in a batch reactor at 450 °C, 60 min. All four plastics gave very high carbon gasification efficiencies (CGE) and hydrogen gasification efficiencies (HGE). Methane was the highest gas component, with a yield of up to 37 mol kg−1LDPE using the 20 wt% RuO2 catalyst. Evaluation of the gas yields, CGE and HGE revealed that the conversion of PS involved thermal degradation, steam reforming and methanation; whereas hydrogenolysis was a possible additional mechanism during the conversion of aliphatic plastics. The process has the benefits of producing a clean-pressurized methane-rich fuel gas as well as cleaning up hydrocarbons-polluted waters.

Collimation of a D-D Neutron Generator for Clinical Implementation of Neutron Stimulated Emission Computed Tomography: a Monte Carlo Study

This work is an investigation into collimator designs for a deuterium-deuterium (DD) neutron generator for an inexpensive and compact neutron imaging system that can be implemented in a hospital. The envisioned application is for a spectroscopic imaging technique called neutron stimulated emission computed tomography (NSECT).

Previous NSECT studies have been performed using a Van-de-Graaff accelerator at the Triangle Universities Nuclear Laboratory (TUNL) in Duke University. This facility has provided invaluable research into the development of NSECT. To transition the current imaging method into a clinically feasible system, there is a need for a high-intensity fast neutron source that can produce collimated beams. The DD neutron generator from Adelphi Technologies Inc. is being explored as a possible candidate to provide the uncollimated neutrons. This DD generator is a compact source that produces 2.5 MeV fast neutrons with intensities of 1012 n/s (4π). The neutron energy is sufficient to excite most isotopes of interest in the body with the exception of carbon and oxygen. However, a special collimator is needed to collimate the 4π neutron emission into a narrow beam. This work describes the development and evaluation of a series of collimator designs to collimate the DD generator for narrow beams suitable for NSECT imaging.

A neutron collimator made of high-density polyethylene (HDPE) and lead was modeled and simulated using the GEANT4 toolkit. The collimator was designed as a 52 x 52 x 52 cm3 HDPE block coupled with 1 cm lead shielding. Non-tapering (cylindrical) and tapering (conical) opening designs were modeled into the collimator to permit passage of neutrons. The shape, size, and geometry of the aperture were varied to assess the effects on the collimated neutron beam. Parameters varied were: inlet diameter (1-5 cm), outlet diameter (1-5 cm), aperture diameter (0.5-1.5 cm), and aperture placement (13-39 cm). For each combination of collimator parameters, the spatial and energy distributions of neutrons and gammas were tracked and analyzed to determine three performance parameters: neutron beam-width, primary neutron flux, and the output quality. To evaluate these parameters, the simulated neutron beams are then regenerated for a NSECT breast scan. Scan involved a realistic breast lesion implanted into an anthropomorphic female phantom.

This work indicates potential for collimating and shielding a DD neutron generator for use in a clinical NSECT system. The proposed collimator designs produced a well-collimated neutron beam that can be used for NSECT breast imaging. The aperture diameter showed a strong correlation to the beam-width, where the collimated neutron beam-width was about 10% larger than the physical aperture diameter. In addition, a collimator opening consisting of a tapering inlet and cylindrical outlet allowed greater neutron throughput when compared to a simple cylindrical opening. The tapering inlet design can allow additional neutron throughput when the neck is placed farther from the source. On the other hand, the tapering designs also decrease output quality (i.e. increase in stray neutrons outside the primary collimated beam). All collimators are cataloged in measures of beam-width, neutron flux, and output quality. For a particular NSECT application, an optimal choice should be based on the collimator specifications listed in this work.

Geosynthetics in Antarctica: performance of a composite barrier system to contain hydrocarbon-contaminated soil after three years in the field

An overview of the design and performance of geosynthetics in composite barrier systems for biopiles used to remediate hydrocarbon-contaminated soil at Casey Station, Antarctica, is presented. Seven instrumented biopiles were constructed over three field seasons. To minimize the risk of hydrocarbon migration to groundwater, composite barrier systems were used (each using different combinations of geosynthetic clay liners (GCLs), high density polyethylene (HDPE) geomembranes (GMB), and geotextiles (GTXs)). One biopile used a co-extruded geomembrane (HDPE with an ethylene vinyl alcohol (EVOH) core). The liner system was subject to a combination of coupled phenomena that could interact and affect the GMB-GCL composite barrier performance. The exposure conditions involved potential freeze-thaw cycling, hydration-desiccation cycles, cation exchange, direct and diffusive exposure to hydrocarbons. The effect of these phenomena was investigated by monitoring GCL and GMB sacrificial coupons. GCL coupons were placed between the main GCL component and the main geomembrane component of the composite liner and GMB coupons placed between the main GMB sheet and the GTX protection layer. Coupons were exhumed from the biopiles each year. The exhumed GCL field moisture content values ranged from 162% to 22%. After three (3) years in the field, GCL coupons that had undergone at least one hydration/desiccation cycle showed no significant change in swell index values or fluid loss values. The measured hydraulic conductivity of exhumed GCL coupons from Biopiles 1 and 2 (3 × 10-11 m s-1) was within the expected range and not significantly different from the values for virgin GCL. GMB coupons exhumed after three years from Biopiles 1 and 2 showed no significant change in oxidative induction time (OIT), melt flow index or tensile properties. Diffusion tests were performed as an index test for establishing the performance of the GMBs as a diffusive barrier to hydrocarbons, with permeation parameters for BTEX contaminants ranging from P g = 0.9-9.2 × 10-13 m2 s-1 for the exhumed GMB (with values depending on the contaminant and GMB). These values were similar to the parameters obtained for virgin GMBs and there was no significant change with field exposure, with GMBs appearing to be performing well.

White-faced storm-petrels Pelagodroma marina predated by gulls as biological monitors of plastic pollution in the pelagic subtropical northeast atlantic

Marine plastic pollution is rapidly growing and is a source of major concern. Seabirds often ingest plastic debris and are increasingly used as biological monitors of plastic pollution. However, virtually no studies have assessed plastics in seabirds in the deep subtropical North Atlantic. We investigated whether remains of white-faced storm-petrels (WFSP) present in gull pellets could be used for biomonitoring. We analysed 263 pellets and 79.0% of these contained plastic debris originating in the digestive tract of WFSP. Pellets with no bird prey did not contain plastics. Most debris were fragments (83.6%) with fewer plastic pellets (8.2%). Light-coloured plastics predominated (71.0%) and the most frequent polymer was HDPE (73.0%). Stable isotopes in toe-nails of WFSP containing many versus no plastics did not differ, indicating no individual specialisation leading to differential plastic ingestion. We suggest WFSP in pellets are highly suitable to monitor the little known pelagic subtropical Northeast Atlantic.