Optimization of the spark plasma sintering processing parameters affecting the properties of polyimide

The present study deals with the optimization of polyimide (PI) mechanical properties, obtained by Spark Plasma Sintering (SPS), by using a method combining Design of Experiments (DOE) with physical, structural, and mechanical characterizations. The effects of SPS parameters such as temperature, pressure, dwell time, and cooling rate on the density, mechanical properties, and structure of PI were investigated. The experimental results revealed that the mechanical properties of the material were optimized by raising the sintering temperature up to 350°C. The optimized SPS processing parameters were a temperature of 350°C, a pressure of 40 MPa, and a dwell time of 5 min. Under these conditions, a relative density of 99.6% was reached within only a few minutes. The corresponding mechanical properties consisted of Young's modulus of 3.43 GPa, a Shore D hardness of 87.3, and a compressive strength of 738 MPa for a maximum compressive strain of 61.8%. Moreover, when working at 320°C and at 100 MPa, an increase in the dwell time was necessary to enhance the properties. Contrary to the other parameters, the cooling rate appeared to be a non‐significant parameter. Finally, correlations between the PI structure and the mechanical properties were made to demonstrate the densification mechanisms. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41542.     

Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.     

Positional distribution of Δ5-acids in triacylglycerols from conifer seeds as determined by partial chemical cleavage

The positional distribution of various Δ5-acids in the seed triacylglycerols from several conifer species has been established after partial chemical degradation with Grignard reagent. The species studied were representative of four conifer families and were specially selected for their particularly high Δ5-acid contents. These species were Taxus baccata (Taxaceae; 5,9-18:2 acid, 11.9%), Larix decidua (Pinaceae; 5,9,12-18:3 acid, 28.5%), Sciadopytis verticillata (Taxodiaceae; 5,11,14-20:3 acid, 16.7%), and Juniperus communis (Cupressaceae; 5,11,14,17-20:4 acid, 19.8%). Calculations from the fatty acid compositions of triacylglycerols and of the mixture of 1,2- and 2,3-diacylglycerols generated by the Grignard reagent indicated that, for the four species, there was a considerable enrichment of Δ5-acids (generally more than ten times) in the 1,3-positions as compared to the 2-position, where Δ5-acids represented always less than 2% of total fatty acids esterified to triacylglycerols. This distribution was practically independent from the species (four families studied), the chainlength (18 or 20 carbon atoms), and the number of ethylenic bonds (two to four) in the Δ5-acids. Similar distributions were established for triacylglycerols from the seeds of three pine species that are available on a ton-scale: Pinus pinea, P. koraiensis, and P. pinaster. These observations confirm and extend previous studies conducted with other conifer species by similar techniques or by ¹³C-nuclear magnetic resonance spectroscopy. Consequently, the almost exclusive location of Δ5-acids in the external positions of triacylglycerols is now well established and appears to be a general feature of conifer seed oils.     

Influence of moisture content on the specific methanogenic activity of dry mesophilic municipal solid waste digestate

The objective of this study was to evaluate the influence of moisture content on the specific methanogenic activity (SMA) of a fresh dry mesophilic digestate from a municipal solid waste digester plant. For this purpose, SMA tests were performed under mesophilic conditions in 500 mL glass bottles of volume used as batch reactors, during a period of 20–25 days. Cellulose, propionate and acetate were used as substrates (5 g_COD kg^?1 digestate) at four different moisture contents, ranging from 65 to 82%. The moisture content strongly influenced the specific methanogenic activity. The highest SMA values were observed at a moisture content of 82% (11.1, 7.8 and 6.0 mg_COD g_VS^?1 d^?1 for cellulose, propionate and acetate spikes, respectively). SMA and moisture content were found to be linearly linked. Dry digestion at low water content is thus detrimental to the biological activity, probably due to physical limitations. Copyright © 2011 Society of Chemical Industry     

Properties of PET/clay nanocomposite films

Polyethylene terephthalate (PET) nanocomposite films were prepared by cast extrusion followed by uniaxial stretching, using chill rolls. Transmission electron microscopy (TEM) and wide angle X‐ray diffraction (WAXD) showed that the clay layers were aligned in the machine direction (MD) in the PET/clay nanocomposite (PCN) films. Differential scanning calorimetry (DSC) showed that PCN films have higher crystallinity than the neat PET films, possibly due to the nucleating role of the silicate layers. The PCN films became hazier as the clay content increased, but the film transparency remained in the acceptable range. Oxygen permeability of the PCN films decreased by 23% compared to the neat PET film. This is comparable with predictions of models proposed in the literature. Silicate incorporation brought about 20% increase in the tensile modulus, while the puncture and tear propagation resistance were reduced, due to brittleness of the PCN films. The measured modulus (1.7 GPa) was somewhat smaller than the values predicted using the Pseudoinclusion model (2.1 GPa). POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Carbon dioxide absorption by monoethanolamine in hollow fiber membrane contactors: A parametric investigation

A mathematical and numerical investigations on the gas–liquid absorption of carbon dioxide in monoethanolamine solutions in a hollow fiber membrane contactor device is described. The reactive absorption mechanism was built based on momentum and mass transport conservation laws in all three compartments involved in the process, i.e., the gas phase, the membrane barrier, and the liquid phase. The liquid absorbing solution flows in the fiber bore in which the velocity is assumed to obey a fully developed laminar flow, and the gas mixture circulates counter‐currently to the liquid flow in the shell side where the velocity is characterized by the Navier‐Stokes momentum balance equations. The average outlet gas and liquid concentrations, the reactive absorption flux, and the gas removal efficiencies are parametrically simulated with operational parameters such as gas flow rate, fresh inlet amine concentrations, and fiber geometrical characteristics. The shell velocity was described by other flow hydrodynamics models besides Navier‐Stokes and their simulated results were favorably compared to experimental data. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

A urine patch framework to simulate nitrogen leaching on New Zealand dairy farms

On New Zealand dairy farms, it is the nitrogen excreted directly onto pasture, particularly urine, that drives nitrogen (N) leaching from the farm. A new framework (UPF: Urine Patch Framework) is presented that post-processes the results of a whole farm model and runs a mechanistic soil model to simulate the urine patches. Two alternative methods to simulate the spatial distribution of urine patches were implemented and compared (Grid: spatially explicit, and Probabilistic: based on the probability of different temporal urination patterns). This paper describes the implementation of these two methods in connection with a Whole Farm Model; and compares the N leaching predictions with observed data. Two examples are provided, one analyzing the impact of urine patch overlap and another, the relative risk of N leaching at different times of urinary N deposition. The model showed good correlation and predictive ability between simulated annual N leaching results and observed data [R² = 94 %, mean relative prediction error (MRPE) = 10 % for Grid and R² = 72 %, MRPE = 20 % for Probabilistic]. The two methods produced similar results across an 8-year period for monthly and annual N leaching (R² = 96 %, MRPE = 10 % and R² = 86 %, MRPE = 8 %; respectively). Only 8 % of the paddock area was covered with multiple urinations during 1 year, but as much as 39 % of the total urine volume was deposited on overlapped patches. Systematically removing all urinary N for 1 month in either May or June reduced N leaching by approximately 20 %. Avoiding urinary N deposition during autumn or early winter could be highly effective in mitigating N leached during the following winter.     

Evaluation of <Emphasis Type="Italic">Rhizopus oryzae</Emphasis> Lipase for the Determination of Regiodistribution in Triacylglycerols with Medium Chain Fatty Acids

The nutritional profile and rheological behaviors of lipids is both due to fatty acid composition and regiodistribution on external and internal positions of triacylglycerol. Actual methods for regiodistribution analysis having some restrictions, there is still a need for investigating a safe, simple and environmentally friendly method for the sn-2 position analysis that could especially be used for the analysis of fats containing medium and short chain fatty acids. The objective of this study was to evaluate the 1,3-selectivity and typoselectivity of Rhizopus oryzae lipase in the presence of short/medium chain fatty acids in partial hydrolysis conditions used for regiodistribution analysis. Structured triacylglycerols containing eight-carbon-chain length fatty acids in the sn -2 position were chemically synthesized using DCC/DMAP coupling agent and purification steps by flash-chromatography. The final product showed very high purity and was used as the substrate for 1,3-selectivity evaluation. Typoselectivity was assessed by investigating partial hydrolysis of equimolar blends of homogeneous TAG. This study confirmed the 1,3-selectivity of Rhizopus oryzae lipase in the hydrolysis conditions used, and revealed that this lipase was less influenced by fatty acids chain length than pancreatic lipase. Considering this, Rhizopus oryzae lipase appeared to be a good candidate for regiodistribution analysis of fats containing medium and short chain fatty acids.     

Surface immobilisation of the sandwich type Na14[Fe4(Ox)4(H2O)2(SbW9O33)2]·60H2O polyoxometalate

A functionalised Fe-substituted Keggin Na₁₄[Fe₄(C₂O₄)₄(H₂O)₂(SbW₉O₃₃)₂]·60H₂O type POM termed “Fe₄Ox₄” has been successfully immobilised onto carbon electrode surfaces through the employment of conducting polypyrrole films and the layer-by-layer (LBL) technique. For the POM doped polypyrrole films the redox systems associated with the POM's tungsten-oxo framework was not apparent upon redox cycling, however a reversible redox couple associated with the Fe^III/II redox system was clearly seen within the pH range 2–7. Organised multilayer assemblies were constructed by the employment of the layer by layer (LBL) technique through alternating anionic Fe₄Ox₄ layers and cationic Ru^II metallodendrimers with poly(diallyldimethylammonium chloride) (PDDA) employed as an initial base layer. Stable redox couples associated with both the Fe^III/II and tungsten-oxo framework, for the Fe₄Ox₄ POM, and the Ru^III/II for the metallodendrimer, were clearly observed upon layer construction and redox switching within the pH domain of 2–7. The resulting multilayer assembly showed good stability towards redox cycling. Further investigations into the multilayer assembly were undertaken by determining it is charge transfer resistance using AC-impedance voltammetry. The layer also showed catalytic ability towards the reduction of H₂O₂ at pH 6.5.     

Volatile lactones from streptomycetes arise via the antimycin biosynthetic pathway

The volatiles released by several streptomycetes were collected by using a closed-loop stripping apparatus (CLSA) and analysed by GC-MS. The obtained headspace extracts of various species contained blastmycinone, a known degradation product of the fungicidal antibiotic, antimycin A(3b), and several unknown derivatives. The suggested structures of these compounds, based on their mass spectra and GC retention indices, were confirmed by comparison to synthetic reference samples. Additional compounds found in the headspace extracts were butenolides formed from the blastmycinones by elimination of the carboxylic acid moiety. Analysis of a gene knockout mutant in the antimycin biosynthetic gene cluster demonstrated that all blastmycinones and butenolides are formed via the antimycin biosynthetic pathway. The structural variation of the blastmycinones identified here is much larger than within the known antimycins, thus suggesting that several antimycin derivatives remain to be discovered.