Investigation of the phase separation of PNIPAM using infrared spectroscopy together with multivariate data analysis

The use of vibrational spectroscopy to investigate complex structural changes in polymers yields chemically rich data, but interpretation can be challenging and subtle but meaningful spectral changes may be missed through visual inspection alone. Multivariate analysis is an efficient approach to gain an oversight of small but systematic spectral differences anywhere within the spectra, providing further insight into structural changes and associated transformation mechanisms. In this study, the novel analytical approach of infrared spectroscopy combined with principal component analysis and Gaussian peak fitting was used to investigate the structural changes in aqueous solutions of a polymer, using poly(N-isopropyl acrylamide) (PNIPAM) in the atactic form and with controlled tacticity as a model system. Subtle spectral changes associated with the dehydration and phase separation upon heating included peak shifts, an area ratio change of the amide I band to the amide II band and formation of a new peak in the amide I band were efficiently detected. Dehydration and phase separation of PNIPAM occurred in two temperature ranges, one for the atactic and one for isotactic rich part, both involving a complex re-organization of the hydrogen bonds and change of the hydration layer. The changes agreed with existing results from other techniques, and new insights were gained into the effect of controlled tacticity on phase transformation behaviour. The study demonstrates that infrared spectroscopy combined with the multivariate analytical method principal component analysis and Gaussian peak fitting is an efficient approach to probing structural change in polymers during heating. The simplicity of the presented approach could find excellent use in analysing and understanding the molecular environment of a range of stimuli-responsive polymers, for instance block or grafted types of polymers, as well as those with controlled tacticity.     

Diagnosis of contamination introduced by ammonia at the cathode in a polymer electrolyte membrane fuel cell

Contamination introduced by impurities from feed streams can impact polymer electrolyte membrane fuel cell performance dramatically. The presence of unwanted trace species, such as CO, H₂S, and NH₃, can adversely affect the function of a fuel cell. It has been reported that the major impact of CO and H₂S contamination on fuel cell performance is kinetic, while the effect of NH₃ contamination is speculated to be mainly membrane conductivity reduction. In this paper, the effect of NH₃ contamination from the cathode side was investigated. The mechanisms of NH₃ contamination were diagnosed based on degradation tests using electrochemical impedance spectroscopy and cyclic voltammetry. The contamination factors investigated included ammonia concentration, operating current, temperature, and relative humidity. The results show that the severity of the adverse effect caused by ammonia contamination was enhanced by increased ammonia concentration, decreased operating temperature, and decreased relative humidity. The performance decay induced by ammonia is attributable to reduced membrane/ionomer conductivity and ammonia adsorption on the catalyst surface, which blocks the active sites and hinders mass transfer.     

Performance of exterior semitransparent PVDF–acrylic coatings

The purpose of this study was to investigate the performance of a semitransparent PVDF–acrylic coating on two wood species: Black spruce and White pine. An accelerated aging test was performed on the PVDF–acrylic coating and the results obtained were compared with those obtained for a water-based acrylic coating. Color changes were found to be more significant for the acrylic coating, especially after 1000 h of exposure, and for the White pine panels. Infrared spectroscopy revealed that the acrylic resin was more affected by the accelerated aging test than the PVDF resin, although X-ray photoelectron spectroscopy revealed that PVDF was slightly affected at the extreme surface (first 10 nm). Star-shaped defects were found at the surface of the White pine panels finished with the PVDF–acrylic coating. Experiments revealed that the PVDF–acrylic coating does not seem to be flexible enough to sustain resin exudation or other stresses.     

Isocyanates,aminoisocyanates and amines from fires—a screening of common materials found in buildings

Isocyanates, aminoisocyanates and amines were quantified from the combustion of 24 different materials or products typically found in buildings. Small‐scale combustion experiments were conducted in the cone calorimeter, where generally well‐ventilated combustion conditions are attained. Measurements were further made in two different full‐scale experiments. Isocyanates and amino‐compounds were sampled using an impinger‐filter sampling system with a reagent solution of di‐n‐butylamine in toluene. Filter and impinger solution were analysed separately using LC‐MS technique. Further the particulate distribution in the smoke gases was determined by impactor technique, and selected gaseous compounds quantified by FTIR. It was found in the small‐scale that isocyanates were produced from the majority of the materials tested. The highest concentration was found for glass wool insulation, and further high concentrations were found for PUR products, particleboard, nitrile rubber and melamine. Lower concentrations were found for wood and cable‐products. Amino‐isocyanates and amines were generally found from PUR products only. The distribution of isocyanates between the particulate‐ and fluid phases varied for the different materials and a tendency to enrichment of particles was seen for some of the materials. Further, when comparing the potential health hazard between isocyanates and other major fire gases (based on NIOSH IDLH‐values) it was found that isocyanates in several cases represented the greatest hazard. Copyright © 2003 John Wiley & Sons, Ltd.     

Microwave-specific heating of crystalline species in nuclear waste glass

The microwave heating of a crystal-free and a partially trevorite-crystallized nuclear waste glass simulant was evaluated. Our results show that a 500-mg monolith of partially crystallized waste glass can be heated from room temperature to above 1600°C within 2 minutes using a single-mode, highly focused, 2.45-GHz microwave, operating at 300 W. Using X-ray diffraction measurements, we show that trevorite is no longer detectable after irradiation and thermal quenching. When a crystal-free analog of the same waste glass simulant composition was exposed to the same microwave radiation, it could not be heated above 450°C regardless of the heating time. The reduction in crystalline content achieved by selectively heating spinels in the presence of glass suggests that microwave-specific heating should be further explored as a technique for remediating crystal accumulation in a glass melt.     

A parametric duration model of the reaction times of drivers distracted by mobile phone conversations

The use of mobile phones while driving is more prevalent among young drivers—a less experienced cohort with elevated crash risk. The objective of this study was to examine and better understand the reaction times of young drivers to a traffic event originating in their peripheral vision whilst engaged in a mobile phone conversation. The CARRS-Q advanced driving simulator was used to test a sample of young drivers on various simulated driving tasks, including an event that originated within the driver's peripheral vision, whereby a pedestrian enters a zebra crossing from a sidewalk. Thirty-two licensed drivers drove the simulator in three phone conditions: baseline (no phone conversation), hands-free and handheld. In addition to driving the simulator each participant completed questionnaires related to driver demographics, driving history, usage of mobile phones while driving, and general mobile phone usage history. The participants were 21–26 years old and split evenly by gender. Drivers’ reaction times to a pedestrian in the zebra crossing were modelled using a parametric accelerated failure time (AFT) duration model with a Weibull distribution. Also tested where two different model specifications to account for the structured heterogeneity arising from the repeated measures experimental design. The Weibull AFT model with gamma heterogeneity was found to be the best fitting model and identified four significant variables influencing the reaction times, including phone condition, driver's age, license type (provisional license holder or not), and self-reported frequency of usage of handheld phones while driving. The reaction times of drivers were more than 40% longer in the distracted condition compared to baseline (not distracted). Moreover, the impairment of reaction times due to mobile phone conversations was almost double for provisional compared to open license holders. A reduction in the ability to detect traffic events in the periphery whilst distracted presents a significant and measurable safety concern that will undoubtedly persist unless mitigated.     

Trend reversal of nitrate in Danish groundwater--a reflection of agricultural practices and nitrogen surpluses since 1950

This paper assesses the long-term development in the oxic groundwater nitrate concentration and nitrogen (N) loss due to intensive farming in Denmark. First, up to 20-year time-series from the national groundwater monitoring network enable a statistically systematic analysis of distribution, trends, and trend reversals in the groundwater nitrate concentration. Second, knowledge about the N surplus in Danish agriculture since 1950 is used as an indicator of the potential loss of N. Third, groundwater recharge CFC (chlorofluorocarbon) age determination allows linking of the first two data sets. The development in the nitrate concentration of oxic groundwater clearly mirrors the development in the national agricultural N surplus, and a corresponding trend reversal is found in groundwater. Regulation and technical improvements in the intensive farming in Denmark have succeeded in decreasing the N surplus by 40% since the mid 1980s, while at the same time maintaining crop yields and increasing the animal production of especially pigs. Trend analyses prove that the youngest (0-15 years old) oxic groundwater shows more pronounced significant downward nitrate trends (44%) than the oldest (25-50 years old) oxic groundwater (9%). This amounts to clear evidence of the effect of reduced nitrate leaching on groundwater nitrate concentrations in Denmark.     

Optimal joint utility based load balancing algorithm for heterogeneous wireless networks

The rapid development of mobile broadband services with continuously increasing traffic volumes has resulted in a number of challenges, including ubiquitous network coverage, high bandwidth, and reliable services for reasonable price, etc. To address these challenges, evolved packet system (EPS) is proposed as the evolution of the packet core network. While resource management and load balancing issues in EPS are discussed in 3GPP standardization, relatively few research works consider mechanism design for load information monitoring and evaluation. Furthermore, even though some load balancing algorithms have been proposed for integrated networks, the load balancing scheme design which achieves the optimization of joint system performance has not been extensively studied. In this paper, an inter-access system anchor based load balancing mechanism is introduced which performs load monitoring and evaluation for access gateways and networks, and an optimal load balancing algorithm is proposed for heterogeneous integrated networks. To characterize the performance of integrated networks, the concept of utility function is introduced and the comprehensive performance of integrated networks which support both single type service and multimedia service is modeled mathematically. Applying vertical handoff as an efficient mechanism for achieving load balancing, the optimal number of handoff users is obtained through solving the optimization problem. Numerical results demonstrate that load balancing between access networks can be achieved, and the optimal number of handoff users corresponding to the maximal joint network utility can be obtained.     

Influence of Loss Model on Design Discharge of Homogeneous Plane

By applying the kinematic wave method to a homogeneous, rectangular overland plane, the influence of the constant and proportional-loss models on the design discharge are examined. The examination shows that with the use of the proportional-loss model, there is no partial-area effect and the design discharge is governed by the full-area contribution. On the other hand, with the use of the constant-loss model, there is no partial-area effect if the loss rate is small. For larger loss rates, there is a partial-area effect; and for this case, the design is complicated, since there is a need to search for the critical storm that governs the partial-area effect. The characteristic of the critical storm is that its rate of decrease in rainfall intensity with duration equals the corresponding rate of increase in the contributing area. The preceding findings are consistent with the design concept in the rational method that uses the proportional-loss model, and the results from earlier studies that used the constant-loss model.