Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, solvent vapor annealing in supported thin films of poly(2‐hydroxyethyl methacrylate)‐block‐poly(methyl methacrylate) [PHEMA‐b‐PMMA] by means of grazing incidence small angle X‐ray scattering (GISAXS) is investigated. A spin‐coated thin film of a lamellar block copolymer is solvent vapor annealed to induce microphase separation and improve the long‐range order of the self‐assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents, which are chosen to be preferential for each block, enables selective formation of ordered lamellae, gyroid, hexagonal, or spherical morphologies from a single‐block copolymer with a fixed volume fraction. The selected microstructure is then kinetically trapped in the dry film by rapid drying. This paper describes what is thought to be the first reported case where in situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram.     

Daily Enteral DHA Supplementation Alleviates Deficiency in Premature Infants

Docosahexaenoic acid (DHA) is an essential fatty acid (FA) important for health and neurodevelopment. Premature infants are at risk of DHA deficiency and circulating levels directly correlate with health outcomes. Most supplementation strategies have focused on increasing DHA content in mother's milk or infant formula. However, extremely premature infants may not reach full feedings for weeks and commercially available parenteral lipid emulsions do not contain preformed DHA, so blood levels decline rapidly after birth. Our objective was to develop a DHA supplementation strategy to overcome these barriers. This double‐blind, randomized, controlled trial determined feasibility, tolerability and efficacy of daily enteral DHA supplementation (50 mg/day) in addition to standard nutrition for preterm infants (24–34 weeks gestational age) beginning in the first week of life. Blood FA levels were analyzed at baseline, full feedings and near discharge in DHA (n = 31) or placebo supplemented (n = 29) preterm infants. Term peers (n = 30) were analyzed for comparison. Preterm infants had lower baseline DHA levels (p < 0.0001). Those receiving DHA had a progressive increase in circulating DHA over time (from 3.33 to 4.09 wt% or 2.88 to 3.55 mol%, p < 0.0001) while placebo‐supplemented infants (receiving standard neonatal nutrition) had no increase over time (from 3.35 to 3.32 wt% or 2.91 to 2.87 mol%). Although levels increased with additional DHA supplementation, preterm infants still had lower blood DHA levels than term peers (4.97 wt% or 4.31 mol%) at discharge (p = 0.0002). No differences in adverse events were observed between the groups. Overall, daily enteral DHA supplementation is feasible and alleviates deficiency in premature infants.     

Effect of polymerization catalyst technology on the melt processing stability of polyethylenes,Part 3: Additives blends performance

This article considers the interaction between additives that occur during the stabilization process. The simultaneous effects of the additives and associated interactions on melt processing stability and processing discoloration were of particular interest. Melt stability is an important factor to consider because physical changes in the processed polymer can occur during the compounding and fabrication steps. Furthermore, discoloration is one of the most important problems affecting commercial polymers. Most discoloration manifests itself as yellowing, especially in the case of polyolefins. Although yellowing can often be associated with degradation processes caused by various agents, such as light or heat, this is not always the case; yellowing can also be due to the interaction of additives in the stabilizer packages. Blends of primary antioxidants (AOs), secondary AOs, and hindered amine light stabilizers have been studied with the intention of further improving stabilization performance together with cost reduction of the stabilized polymer. Although synergism between AOs and a stabilizer is fairly common, antagonism was also observed in terms of melt flow protection and in color stability in some of the AOs tested. The effects of a range of thermal and light stabilizers on the melt stability (investigated via multiple pass extrusion) and color stability of three different polyethylenes (PEs) were examined. The PEs varied in terms of the catalyst system used to synthesize the polymers and included a high‐density polyethylene (HDPE) produced by using a chromium‐based Phillips catalyst and two linear low‐density polyethylenes (LLDPEs) produced via chromium‐based metallocene and titanium‐based Ziegler‐Natta catalysts. The apparent lack of influence of polymerization catalyst system on the mode of stabilizer interaction should lead to the reassessment of stabilizer formulation strategies in relation to PE type/catalyst system and associated commercial/economic considerations. J. VINYL ADDIT. TECHNOL., 22:117–127, 2016. © 2014 Society of Plastics Engineers     

Correlating Molecular Structure to the Behavior of Linear Styrene–Butadiene Viscosity Modifiers

The effect of linear styrene–butadiene polymer structure on the temperature–viscosity behavior of model polymer-base oil solutions is investigated using molecular dynamics simulations. Simulations of alternating, random, and block styrene–butadiene polymers in a dodecane solvent are used to calculate viscosity at 40 and 100 °C, reference temperatures for characterizing their function as viscosity modifiers. Mechanisms underlying this function are explored by quantifying the radius of gyration and intramolecular interactions of the polymers at the same reference temperatures. The block styrene–butadiene configuration exhibits the least change in viscosity with temperature, characteristic of a good viscosity modifier or viscosity index improver, and the behavior is correlated to the ability of this structure to form smaller coils with more intramolecular interactions at lower temperatures and then expand as temperature is increased. The results indicate that there is a correlation between styrene–butadiene polymer structure, additive function, and the mechanisms underlying that function.     

Influence of caring youth sport contexts on efficacy-related beliefs and social behaviors.

Understanding what factors influence positive youth development has been advocated by youth development researchers (P. L. Benson, 2006; J. S. Eccles & J. A. Gootman, 2002). Consequently, the purpose of this study was to examine whether perceptions of a caring youth sport context influenced prosocial and antisocial behavior through efficacy-related beliefs, that is, positive and negative affective self-regulatory efficacy (ASRE) and empathic self-efficacy (ESE). Multiethnic youths taking part in summer sport programs (N = 395) completed a questionnaire that measured perceptions of the caring climate, ESE, ASRE, and social behavior. Structural equation modeling was used to test whether ASRE and ESE mediated the relationship between caring and social behaviors. Findings revealed that perceptions of caring positively predicted ASRE and ESE. In turn, positive ASRE positively predicted ESE. Prosocial behaviors were positively linked to ESE, whereas antisocial behaviors were negatively predicted by positive ASRE. The results suggest that caring influences prosocial and antisocial behavior because such contexts develop youths' ability to monitor, manage, and control positive affect, which in turn enhances their belief in their ability to empathize. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

An examination of the relationship between workload and fatigue within and across consecutive days of work: Is the relationship static or dynamic?

Cognitive–energetical theories of information processing were used to generate predictions regarding the relationship between perceived workload and fatigue within and across consecutive days of work. Repeated measures were taken aboard a naval vessel from a sample of 20 Navy patrol vessel crew members during nonroutine and routine patrols. The hypotheses were tested through growth curve modeling. There was a nonmonotonic relationship between workload and fatigue in the routine patrol; moderate workload was associated with the lowest fatigue. The relationship between workload and fatigue changed over consecutive days in the nonroutine patrol. At the beginning of the patrol, low workload was associated with fatigue. At the end of the patrol, high workload was associated with fatigue. These results suggest that the optimal level of workload can change over time and thus have implications for the management of fatigue, particularly where prolonged operations are involved. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Thermostat settings in English houses: No evidence of change between 1984 and 2007

Rising demand temperatures are widely blamed for UK home energy use not declining over time despite the increased efficiency of dwelling envelopes and heating technologies. The hypothesis that thermostat settings have risen over time is tested using a repeated cross-sectional social survey of owners of centrally heated English houses. No statistical evidence for changes in reported thermostat settings between 1984 and 2007 is found.