Photo-mediated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reactions for forming polymer networks as shape memory materials

The formation of polymer networks polymerized with the Copper (I) – catalyzed azide – alkyne cycloaddition (CuAAC) click reaction is described along with their accompanying utilization as shape memory polymers. Due to the click nature of the reaction and the synthetic accessibility of azide and alkyne functional-monomers, the polymer architecture was readily controlled through monomer design to manipulate crosslink density, ability for further functionalization, and the glass transition temperature (55–114 °C). Free strain recovery is used to quantify the shape memory properties of a model CuAAC network resulting in excellent shape fixity and recovery of 99%. The step growth nature of this polymerization results in homogenous network formation with narrow glass transitions ranges having half widths of the transition close to 15 °C for these materials resulting in shape recovery sharpness of 3.9%/°C in a model system comparable to similarly crosslinked chain growth polymers. Utilization of the CuAAC reaction to form shape memory materials opens a range of possibilities and behaviors that are not readily achieved in other shape memory materials such as (meth) acrylates, thiol-ene, thiol-Michael, and poly(caprolactone) based shape memory materials.     

13.3% efficient solution deposited Cu(In,Ga)Se2 solar cells processed with different sodium salt sources

In this work, we obtain the highest reported power conversion efficiency (13.3%) for sulfur‐free CIGSe solar cells by solution processing. Intentional sodium incorporation is achieved directly by dissolving sodium salts in the ink. The effect on solar cell properties of three sodium sources is investigated: NaCl, NaHCO₂, and NaSCN. A comparison is made with absorbers grown on soda‐lime glass substrates and in the absence of sodium sources. The incorporation via sodium salts yields significantly better results, which is attributed to enhanced‐sodium availability. A comparison with identically annealed sputtered metal precursor layers capable of delivering 15.1% module efficiency suggests that the cell results are limited by the selenization procedure. Copyright © 2015 John Wiley & Sons, Ltd.     

Fine limestone additions to regulate setting in high volume fly ash mixtures

High volume fly ash (HVFA) concrete mixtures are being considered more frequently due to their cost and sustainability advantages. While the long term performance of these HVFA concretes typically meets or exceeds that of conventional concretes, their early age performance is often characterized by excessive retardation of the hydration reactions, delayed setting times, and low strengths. Extending an HVFA mixture to a ternary blend that incorporates a fine limestone powder may provide a viable solution to these deficiencies, particularly the hydration retardation and setting issues. In this paper, a nano-limestone powder and two other limestone fillers of increasing median particle size (4.4 μm and 16.4 μm) are investigated for their propensity to accelerate early age reactions and reduce setting times in a Class C fly ash/cement blend. The fineness of the limestone has measurable effects on its efficacy in accelerating hydration and decreasing setting times. Companion specimens prepared with a fine silica powder suggest that the fine limestone may act favorably through both a physical and a chemical mechanism. Isothermal calorimetry and Vicat needle penetration measurements on pastes are accompanied by strength measurements on mortars, to verify that the limestone powder substitutions are not negatively impacting strength development. A linear relationship with a reasonable correlation is found to exist between 1 d and 7 d compressive strengths of mortars and their accompanying cumulative heat release values as determined using isothermal calorimetry.     

Active dry Saccharomyces cerevisiae can alleviate the effect of subacute ruminal acidosis in lactating dairy cows

The objective of the study was to determine the effect of active dry Saccharomyces cerevisiae (ADSC) supplementation on dry matter intake, milk yield, milk components, ruminal pH, and microbial community during a dietary regimen that leads to subacute ruminal acidosis (SARA). Sixteen multiparous, rumen-cannulated lactating Holstein cows were randomly assigned to 1 of 2 dietary treatments that included ADSC (Biomate; AB Vista, Marlborough, UK; 8 × 10¹⁰ cfu/head per day) or control. During wk 1 to 6, all cows received a high-forage (HF) diet (77:23, forage:concentrate). Cows were then abruptly switched during wk 7 to a high-grain (HG) diet (49:51, forage:concentrate) and remained on the HG until the end of wk 10. Feed intake and milk yields were recorded daily. Ruminal pH was recorded continuously using an indwelling system for 1 to 2 d per week during the pre-experimental phase, and wk 6, 7, and 10. Ruminal digesta samples were collected at the end of the experiment and analyzed for relative change in microbial communities using real-time quantitative PCR. Cows were considered to have SARA if the duration below pH 5.6 was ≥300 min/d. Ruminal pH during wk 6 (HF plateau) was not different across treatments (15 ± 46 min/d at pH <5.6). The dietary regimen successfully induced SARA during wk 7 (transition from HF to HG diet), and ruminal pH (551 ± 46 min/d at pH <5.6) was not different across treatments. However, cows receiving ADSC had an improved ruminal pH (122 ± 57 vs. 321 ± 53 min/d at pH <5.6) during wk 10 (HG plateau) compared with control. Additionally, cows receiving ADSC had a better dry matter intake (23.3 ± 0.66 vs. 21.6 ± 0.61 kg/d) and 4% fat-corrected milk yield (29.6 ± 1.2 vs. 26.5 ± 1.2 kg/d) than control cows during the HG phase (wk 8 to 10). During HG feeding, cows receiving ADSC had greater total volatile fatty acid and propionate concentrations (175 ± 7.5 vs. 154 ± 7.5 and 117 ± 6.1 vs. 94 ± 5.7 mM for ADSC and control, respectively) and lower acetate:propionate ratio (0.26 ± 0.5 vs. 0.36 ± 0.05 for ADSC and control, respectively). Microbial analyses conducted on samples collected during wk 10 showed that cows supplemented with S. cerevisiae had a 9-fold, 2-fold, 6-fold, 1.3-fold, and 8-fold increase in S. cerevisiae, Fibrobacter succinogenes, Anaerovibrio lipolytica, Ruminococcus albus, and anaerobic fungi, respectively, which suggested an increase in cellulolytic microbes within the rumen. Cows supplemented with ADSC had 2.2-fold reduction in Prevotella albensis, which is a gram-negative bacterium predominant during SARA. Prevotella spp. are suggested to be an important source of lipopolysaccharide responsible for inflammation within the rumen. Cows supplemented with ADSC had a 2.3-fold increase in Streptococcus bovis and a 12-fold reduction in Megasphaera elsdenii. The reduction in M. elsdenii may reflect lower concentration of lactic acid within the rumen for ADSC cows. In conclusion, ADSC supplementation to dairy cows was demonstrated to alleviate the condition of SARA caused by abrupt dietary changes from HF to HG, and can potentially improve rumen function, as indicated by greater numbers of cellulolytic microorganisms within the rumen.     

The Effect of Mn-rich Precipitates on the Strength of AZ31 Extrudates

The commercial magnesium alloy AZ31 has been subjected to a range of solution treatment regimes. These have then been extruded and their microstructure, texture, and precipitate populations characterized along with their mechanical properties. During the solution treatment, Mn-enriched particles develop and these remain largely unchanged throughout subsequent processing steps. A direct link between grain size and texture has been found, with coarser-grained specimens showing sharper textures. VPSC modeling has been used to quantify the effect of texture on the tensile yield strength, and it has been found that sharper textures have larger tensile yield strengths. Since coarser grain sizes have reduced Hall–Petch hardening, but have an additional texture-strengthening component, a region on the Hall–Petch plot for tension has been identified in which there is an insensitivity of strength to grain size. This has been quantitatively modeled and a texture-modified Hall–Petch plot for tension has been developed. The Mn-rich particles have also been shown to provide precipitate strengthening to the alloy of up to 40 MPa. The compressive behavior was clearer, with the compressive yield strength being directly correlated to grain size and unaffected by texture or precipitation hardening.