Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

Biobased flexible polyurethane foams manufactured from lactide-based polyester-ether polyols for automotive applications

In this study, biobased polyester-ether polyols derived from meso-lactide and dimer acids were evaluated for flexible polyurethane foams (PUF) applications. Initially, the catalyst concentration was optimized for the biobased PUF containing 30% of biobased polyol (70% petroleum-based polyol). Then, the same formulation was used for biobased PUF synthesis containing 10%–40% of biobased polyols. The performance of biobased PUF was compared with the performance of the control foam made with 100% petroleum-based polyol. The characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased PUF were determined. The biobased PUF were evaluated for the mechanical (tensile and compressive) and morphological properties. As the wet compression set is important for automotive applications, it was measured for all biobased PUF. The thermal degradation behavior of biobased PUF was also evaluated and compared with the control foam. The effect of different hydroxyl and acid values of polyols on the mechanical properties of biobased PUF is also discussed. The miscibility of all components of PUF formulations is crucial in order to produce a foam with uniform properties. Thus, the miscibility of biobased polyols with commercial petroleum-based polyol was studied.     

Crystal structures and phase transformation of deuterated lithium imide, Li2ND

Half-Heusler compounds of Sn-doped TiCoSb “TiCoSn_xSb_1−x (x = 0.0, 0.01, and 0.05)” were prepared and their thermoelectric properties were measured above room temperature. From the EDX analysis, all the samples have three phases: the TiCoSn_xSb_1−x, Co-rich, and Ti-rich phases. The values of the thermoelectric power increase with Sn doping, and a positive thermoelectric power is obtained in the sample of TiCoSn_0.05Sb_0.95. The thermal conductivity decreases both with increasing temperature and with Sn content. The maximum value of ZT for p-type material is 0.030 at 988 K in the sample of TiCoSn_0.05Sb_0.95.     

Influence of diurnal and seasonal temperature variations on the detection of corrosion in reinforced concrete by acoustic emission

Chloride rich reinforced concrete prisms were coupled to chloride-free prisms and exposed to diurnal and seasonal temperature cycles typical of those found in the UK. Acoustic emissions (AE) and galvanic currents were continuously monitored and correlated with ambient temperature. AE and galvanic currents were found to emulate the evolution of temperature in the diurnal cycles, although no specific relationship between AE and galvanic current could be obtained. The influence of seasonal variations in galvanic current had no obvious influence on AE Energy per second over the range of corrosion rates studied. The findings suggest that AE is more sensitive to short term (diurnal) changes in corrosion rates than the longer (seasonal) effects. It was hypothesised that this is due to transitory changes in the internal microclimate of the concrete.     

Connectionist simulation of quantification skills

The study of numerical abilities, and how they are acquired, is being used to explore the continuity between ontogenesis and environmental learning. One technique that proves useful in this exploration is the artificial simulation of numerical abilities with neural networks, using different learning paradigms to explore development. A neural network simulation of subitization, sometimes referred to as visual enumeration, and of counting, a recurrent operation, has been developed using the so-called multi-net architecture. Our numerical ability simulations use two or more neural networks combining supervised and unsupervised learning techniques to model subitization and counting. Subitization has been simulated using networks employing unsupervised self-organizing learning, the results of which agree with infant subitization experiments and are comparable with supervised neural network simulations of subitization reported in the literature. Counting has been simulated using a multi-net system of supervised static and recurrent backpropagation networks that learn their individual tasks within an unsupervised, competitive framework. The developmental profile of the counting simulation shows similarities to that of children learning to count and demonstrates how neural networks can learn how to be combined together in a process modelling development.     

Weep hole inspection by circumferential creeping waves

This paper reports the development of a novel ultrasonic inspection technique that detects radial fatigue cracks on the far side of thin airframe stiffener ‘weep’ holes. These cracks are located on the upper part of the weep hole (12 o'clock position), away from the lower skin of the wing. Cracks in this position are not readily detectable by conventional ultrasonic inspection techniques, particularly for short cracks. A special technique using circumferential creeping waves was adapted to inspect for these cracks. The conventional creeping wave technique experiences a strong specular reflection from the near surface of the hole that masks the creeping wave signal that arrives later in time. In order to overcome this difficulty, a split-aperture (two-element) transducer was used that resulted in the specular and creeping wave echoes being approximately equal in magnitude. The two separate transducers allowed us to alternate between pulse-echo and pitch-catch modes of operation with a resulting improvement in detection sensitivity. In the case of 0.25-inch-diameter weep holes, optimum sensitivity was calculated to be around 5 MHz. The detection threshold was found to be approximately 0.003 inches and the signal saturated at crack lengths in excess of 0.020 inches. The original paint and surface finish had no substantial adverse effects on the technique's sensitivity. Similarly, changing the weep hole diameter or chamfer conditions did not significantly affect the technique's performance. These results were obtained using specimens with both machined notches and real fatigue cracks.     

Tourism as tragedy? Common problems with water in post-revolutionary Nicaragua

This paper examines the increased demand placed on limited water resources by a rapidly growing tourism sector in Playa Gigante, Nicaragua. Results from field campaigns suggest that recharge of the local aquifer may not meet burgeoning tourism demands for water. This paper also points to initial conflicts over water between locals and tourism operations, which are further complicated by ineffective implementation of national water policies and the common pool nature of groundwater. The conclusion discusses the need for more extensive research and better implementation of water policy through community governance and collaboration.