Transport properties of natural gas through polyethylene nanocomposites at high temperature and pressure

Four titanium(IV) alkoxides, namely: Ti(IV) n-propoxide (1), Ti(IV) n-butoxide (2), Ti(IV) tert-butoxide (3), and Ti(IV) 2-ethylhexoxide (4), have been used as initiators in the bulk ring-opening polymerization (ROP) of ??-caprolactone (??-CL). The influence of the alkoxide group on the course of the ROP of ??-CL was investigated by means of ¹H-NMR and differential scanning calorimetry (DSC). The ¹H-NMR spectra confirmed that the ROP reaction of ??-CL proceeded via the widely accepted coordination-insertion mechanism for each of the four initiators. Isoconversional methods have been used to evaluate non-isothermal DSC data via the equations of Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW). The kinetic studies showed that the polymerization rate for the four initiators (1-4) was in the order of 1?>?2????4?>?3. The lowest activation energies (40?C47, 42?C44, and 49?C52?kJ/mol for the Friedman, KAS and OFW methods respectively) were found in the polymerizations using Ti(IV) n-propoxide (1), while the highest activation energies (84?C107, 77?C87, and 80?C91?kJ/mol for the Friedman, KAS and OFW methods respectively) were obtained using Ti(IV) tert-butoxide (3). Differences in the rates of polymerization and the activation energies amongst the four initiators appeared to be governed mainly by the different degrees of steric hindrance in the initiator structure. These results represent important findings regarding the steric influence of the alkoxide groups on the kinetics of the ROP of ??-CL initiated by titanium(IV) alkoxides.     

Variation of Brominated Indoles and Terpenoids Within Single and Different Colonies of the Marine Bryozoan Flustra foliacea

The variation of the brominated indole and diterpenoid content within single and different colonies of the bryozoan Flustra foliacea was investigated. The secondary metabolite profile and concentrations of individual components of F. foliacea samples were established using GC-MS. Samples from 17 different collecting sites were analyzed. The alkaloid and diterpene composition of F. foliacea varied greatly depending upon the site of collection. Investigation of F. foliacea samples from a single site (Helgoland, North Sea) over a period of time showed that the alkaloid and diterpenoid profile remained constant, however concentrations of individual components varied significantly. The alkaloid and diterpenoid composition of different segments of a single colony was found to be constant. Only small differences could be detected in the essential oil composition of different colonies and segments of single colonies of F. foliacea. Two of the F. foliacea alkaloids were found in the gastropods Hydrobia ulva and Gibbula cinerea, and one alkaloid in the common starfish Asteria rubens, all collected from the surface of the bryozoan.     

Singlet oxygen microscope: from phase-separated polymers to single biological cells

The lowest excited electronic state of molecular oxygen, singlet molecular oxygen (a1Deltag), is an intermediate in many chemical and biological processes. Tools and methods have been developed to create singlet-oxygen-based optical images of heterogeneous samples that range from phase-separated polymers to biological cells. Such images provide unique insight into a variety of oxygen-dependent phenomena, including the photoinitiated death of cells.     

Modification of margarine fats by enzymatic interesterification: Evaluation of a solid-fat-content-based exponential model with two groups of oil blends

Lipozyme TL IM-catalyzed interesterification for the modification of margarine fats was carried out in a batch reactor at 70°C with a lipase dosage of 4%. Solid fat content (SFC) was used to monitor the reaction progress. Lipase-catalyzed interesterification, which led to changes in the SFC, was assumed to be a first-order reversible reaction. Accordingly, the change in SFC vs. reaction time was described by an exponential model. The model contained three parameters, each with a particular physical or chemical meaning: (i) the initial SFC (SFC₀), (ii) the change in SFC (ΔSFC) from the initial to the equilibrium state, and (iii) the reaction rate constant value (k). SFC_o and ΔSFC were related to only the types of blends and the blend ratios. The rate constant k was related to lipase activity on a given oil blend. Evaluation of the model was carried out with two groups of oil blends, i.e., palm stearin/coconut oil in weight ratios of 90∶10, 80∶20, and 70∶30, and soybean oil/fully hydrogenated soybean oil in weight ratios of 80∶20, 65∶35, and 50∶50. Correlation coefficients higher than 0.99 between the experimental and predicted values were observed for SFC at temperatures above 30°C. The model is useful for predicting changes in the SFC during lipase-catalyzed interesterification with a selected group of oil blends. It also can be used to control the process when particular SFC values are targeted.     

Effect of biogas technology on nutrient flows for small- and medium-scale pig farms in Vietnam

Increased demand for meat products has led to increased livestock production in Vietnam, which now risks environmental pollution from inappropriate animal manure management on livestock farms. Biogas technology is generally considered an efficient solution for such farms to produce renewable biofuel for use in the household and to reduce the pollution impact from animal waste. However, with biogas technology, farmers may reduce their use of manure for fertilising crops. This field survey investigated nutrient flows on small- and medium-scale livestock farms with and without biogas in Northern Vietnam, in order to identify existing problems and possibilities for sustainable livestock production. A field survey was conducted on 12 pig farms with biogas and 12 pig farms without biogas in Quoc Oai district, Hanoi city. In general, the non-biogas pig farms used on average 3.8 ton compost and 3.1 ton fresh solid manure ha^?1?crop^?1 for each of three crops typically grown per year on their arable land. They discharged on average 16?% of the total manure produced into the environment in liquid form through the public sewage system. On biogas pig farms, the use of fresh solid manure for crops and discharge of liquid manure was lower, as manure was used to produce biogas. However, excessive use of washing water on several of these farms resulted in very dilute slurry (solid manure:water ratio 1:11) entering the biogas digester. This lowered the retention time in the digester (below the optimum range of 35?C55?days), leading to low biogas production rates and possible accumulation of sediment. The digestate was also highly diluted and hence difficult and costly to transport and apply to crops, so it was largely (60?%) discharged to the environment. The input volume of washing water should therefore be reduced to a ratio of 1:5. For better sustainability, appropriate technologies are needed to absorb nutrients from the digestate before discharge and to recycle these nutrients to crops.     

MgAl2O4-Spinel Synthesized by High-Energy Ball Milling and Reaction Sintering

A new way to prepare magnesia-alumina-spinel was investigated making use of a mixed powder system of MgO and metallic Al-3 wt% Mg. Intensive ball milling was applied which provides the formation of new powder particles as composite of both components in intimate contact. The new configuration of the particles had a significant impact on the reaction sintering behavior leading to single phase spinel microstructures at moderate temperatures below 1400°C. Optimized milling of the powder mixture was therefore required providing reduced crystallite sizes and strongly enlarged interfacial area shared by the reacting components. The optimal milling time was identified by the complete reaction of the starting powders to spinel during sintering. Shorter milling times led to incomplete reactions and longer milling times contaminated the milling product by debris from the milling tools. The amount of interfaces generated by the intimate mixing dominated the sintering reaction kinetics whereas the specific surfaces area was of secondary importance.     

TPA‐PPEs – New alternating donor copolymers for potential application in photovoltaic devices

A series of phenyleneethynylene copolymers with triphenylamine units as hole‐transporting moieties (TPA‐PPEs) were synthesized by the palladium‐catalyzed cross‐coupling polycondensation of diethynyltriphenylamines and selected dihalogen comonomers, for instance substituted benzene, thiophene, benzothiadiazole, or anthracene. Incorporation of the electron‐rich amino group into the PPE backbone does not interrupt the main chain conjugation. Furthermore, it has a decreasing effect on the oxidation potential, thus makes these polymers interesting as hole‐injection/hole‐transporting materials. The chemical structure of the new alternating copolymers was confirmed by ¹H and ¹³C NMR spectroscopy and elemental analysis and gel‐permeation chromatography (GPC; THF, M_n ≈ 15,000–30,000 g/mol) was conducted. Furthermore, their optical properties were investigated by UV/vis spectroscopy. The TPA‐PPEs exhibit absorption maxima at around 400 nm (π‐π*), except anthracene containing copolymer 3f (λ_max = 514 nm in THF) and benzothiadiazole containing one 3g (λ_max = 503 nm in THF). The TPA copolymers have oxidation potentials about 1.1 V (Ag/AgCl). They are good photoconducting materials ( 3a : I_Photo = 4 × 10^?10 A at 425 nm (400 V), 3g : I_Photo = 1.3 × 10^?11 A at λ_max = 500 nm (20 V)) and show emission after excitation at around 450 nm (560 nm 3f ). Their application in nonoptimized polymer solar cells (bulk heterojunction) led to power conversion efficiencies of around 1–1.8% after illumination with 100 mW/cm² of AM1.5. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Holistic process planning chain for robot machining

Today, machining of large, integral constructed structural parts requires expensive machining centers. In contrast, modern industrial robots are suitable for a wide field of applications and are characterized large working spaces and low capital investment. Therefore, they provide high economical potential for machining applications in aerospace industry, especially for the machining of near to shape pre-products like extruded profiles. However, their constructive characteristics like low stiffness and high sensitivity to vibrations lead to disadvantages compared with conventional machining centers and have to be considered during process planning. Therefore, several methods for offline and online optimization of robot machining processes were developed and integrated in a new process chain for manufacturing of structural fuselage parts. Thereby, the conventional CAD–CAM process planning chain was extended with simulation based analysis and optimization methods and a load-depending trajectory planning. These methods for offline process optimization within this novel process chain are presented in this paper.