Interpretation of long-chain structure from dilute solution properties of ultrahigh molecular weight polymers

Summary Systematic studies on solution properties of ultrahigh molecular weight polymers showed the existence of some special features as compared to usual length polymers. The paper discusses the possible appearance of branched structures in the polymerization process, structures able to influence the mentioned features. From experimental data on poly(methyl methacrylate), poly(butyl methacrylate) and polyacrylonitrile it appears that branching can be excluded, and the very high molecular weight domain considered may be responsible for the modifications observed in the molecular weight dependences on 2>, A₂ or [].     

An Interactive Tool for the Optimization of Freeze-Drying Cycles Based on Quality Criteria

Among existing dehydration methods, freeze-drying has unique benefits for the stabilization and preservation of biological activity of pharmaceutical products but remains an expensive and time-consuming process. A user-friendly software tool was developed, allowing for interactive selection of process operating condition profiles in order to maximize process productivity while insuring product quality preservation. The software is based on a dynamic, one-dimensional heat and mass transfer model, which can accurately represent both the primary and secondary drying stages and the gradual transition between them. The model was validated in a wide range of operating conditions: ? 25 to + 25°C shelf temperature and 10 to 34 Pa total pressure. By comparing a reference sucrose solution with a formulated pharmaceutical product containing polyvinylpyrrolidone (PVP), it is shown that controlling product properties such as glass transition temperature and sorption isotherm can reduce the minimum achievable cycle duration by 12 h (33%).     

Flow Properties of Ultrahigh-Molecular-Weight Poly(Methyl Methacrylate) in Semidilute Solutions

The article presents some Theological results obtained on a large domain of shear rates for semidilute solutions of ultrahigh-molecular-weight poly(methyl methacrylate) at different concentrations. The observed unusual behavior was explained as being due to the flow instabilities of long-chain polymers in an entangled state.     

Wood‐fiber/high‐density‐polyethylene composites: Coupling agent performance

The coupling efficiency of seven coupling agents in wood–polymer composites (WPC) was investigated in this study. The improvement on the interfacial bonding strength, flexural modulus, and other mechanical properties of the resultant wood fiber/high‐density polyethylene (HDPE) composites was mainly related to the coupling agent type, function groups, molecular weight, concentration, and chain structure. As a coupling agent, maleated polyethylene (MAPE) had a better performance in WPC than oxidized polyethylene (OPE) and pure polyethylene (PPE) because of its stronger interfacial bonding. A combination of the acid number, molecular weight, and concentration of coupling agents had a significant effect on the interfacial bonding in WPC. The coupling agents with a high molecular weight, moderate acid number, and low concentration level were preferred to improve interfacial adhesion in WPC. The backbone structure of coupling agents also affected the interfacial bonding strength. Compared with the untreated composites, modified composites improved the interfacial bonding strength by 140% on maximum and the flexural storage modulus by 29%. According to the statistical analysis, 226D and 100D were the best of the seven coupling agents. The coupling agent performance was illustrated with the brush, switch, and amorphous structures. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 93–102, 2005     

Pullulan: A versatile coating agent for superparamagnetic iron oxide nanoparticles

Ultrasmall superparamagnetic iron oxide (Fe₃O₄) nanoparticles coated by biocompatible pullulan (Pu‐USPIO) with sizes below 10 nm and having a magnetite core and a hydrophilic outer shell of pullulan were prepared. The formed Pu‐USPIOs were thoroughly characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, atomic force microscopy, and small‐angle X‐ray scattering experiments. The content of magnetic nanoparticles embedded into the pullulan matrix was determined by thermogravimetric analysis. Vibrating sample magnetometry analysis was used to evaluate the magnetic properties of the Pu‐USPIO samples. Because of the presence of pullulan, these nanoparticles could be conditioned in many versatile forms, from a clear solution to magnetic films, for potential applications, including magnetic hyperthermia mediators. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42926.     

Binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] nanocomposites: formation, characterization and catalytic performance in partial ethanol oxidation

Cuprous oxide agglomerates composed of 4-10 nm Cu2O nanoparticles were deposited on multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNTs to give binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] composites. Di-aqua-bis[2-(methoxyimino)propanoato]copper Cu[O2CCCH3NOMe](2)·2H2O 1 in DMF was used as single source precursor for the deposition of nanoscaled Cu2O. The precursor decomposes either in air or under argon to yield CuO2 by in situ redox reaction. Thermogravimetric coupled mass spectroscopic analysis (TG-MS) of 1 revealed that methanol formed during the decomposition of 1 acts as a potential in situ reducing agent. Scanning electron microscopy (SEM) of the binary [Cu2O/MWCNT] nano-composite shows an increase of cuprous oxide loading depending on the precursor amount, along the periphery of the MWCNTs as well as formation of larger particle agglomerates. Transmission electron microscopy (TEM) of the sample shows crystalline domains of size 4-10 nm surrounded by an amorphous region within the larger particles. SEM and TEM of ternary [Cu2O/ZnO/MWCNT] clearly reveal that Cu2O nanoparticles are primarily deposited on ZnO rather than on MWCNTs. The catalytic activities of the [Cu2O/MWCNT] and [Cu2O/ZnO/MWCNT] binary and ternary composites were studied for the selective partial oxidation of ethanol to acetaldehyde with molecular oxygen. While using binary [Cu2O/MWCNT] (13.8 wt% Cu) as catalyst, acetaldehyde was obtained with a yield of 87% at 355 °C (selectivity 96% and conversion 91%). When nanoscale ZnO is present, the resulting [Cu2O/ZnO/MWCNT] composite shows preferential hydrogen and CO2 formation due to the fact that the dehydrogenation and total oxidation pathway is more favoured compared to the binary composite. Significant morphological changes of the catalyst during the catalytic process were observed.     

Study of the Catalytic Activity–Semiconductive Properties Relationship For BaTiO<Subscript>3</Subscript> and PbTiO<Subscript>3</Subscript> Perovskites,Catalysts for Methane Combustion

Abstract  

The electrical conductivity of barium and lead perovskites used as catalysts for the total oxidation of methane, has been measured under nitrogen, methane–nitrogen mixture, air and methane–air mixture (reaction mixture) at the catalytic reaction temperature. The two compounds appeared to be p-type semiconductors under air with positive holes as the main charge carriers but became n-type when contacted with methane–nitrogen mixture. Their conductivities differ by 1.5 orders of magnitude as n-type semiconductors and by three orders of magnitude when being p-type semiconductors. These results explained the difference in the catalytic activity encountered on the two solids. The alkane activation was proposed to be related in both cases to the p-type semiconducting properties of the solids, likely through hydrogen abstraction by a surface O⁻ species, forming a CH₃^• radical. The overall reaction mechanism on both perovskites can be assimilated to a Mars and van Krevelen mechanism.     

l-Lactic acid biosensor based on multi-layered graphene

Pristine graphene platelets and graphene oxide were used as electrode modifiers, aiming the investigation of their electrochemical efficacy towards β-nicotinamide adenine dinucleotide (NADH). The electrochemical detection of NADH is one of the most studied areas of bioelectroanalysis because of the ubiquity of NAD(P)H-based enzymatic reactions in nature. Commercially available graphene and laboratory prepared graphene oxide were used to modify glassy carbon electrodes and the behaviour of such modified electrodes against potassium ferricyanide (III) and NADH was reported. Relying on the graphene-modified transducer, l-lactic dehydrogenase (l-LDH) was successfully immobilised in a 1 % Nafion^® membrane. The developed biosensor, working at +250 mV versus Ag/AgCl reference electrode, was used to assess l-lactic acid in four different types of yogurts, revealing an l-lactic acid concentration ranging between 0.3 and 0.6 %.     

Chemical oxidation of residual carbon from ZnAl2O4 powders prepared by combustion synthesis

The removal of carbon residue from ZnAl₂O₄ nanopowders by annealing at 500–800 °C leads to a decrease of specific surface area from 228.1 m²/g to 47.6 m²/g. At the same time, the average crystallite size increased from 5.1 nm to 14.9 nm. In order to overcome these drawbacks, a new solution for removing the carbon residue has been suggested: chemical oxidation using hydrogen peroxide. In terms of carbon removal, a H₂O₂ treatment for 8 h at 107 °C proved to be equivalent to a heat treatment of 1 h at 600 °C. The benefits of chemical oxidation over thermal oxidation were obvious. The specific surface area was much larger (188.1 m²/g) in the case of the powder treated with H₂O₂. The average crystallite size (5.8 nm) of ZnAl₂O₄ powder treated with H₂O₂ was smaller than the crystallite size (8.2 nm) of the ZnAl₂O₄ powder annealed at 600 °C.     

Neural network modeling of the preparation process of a siloxane‐organic polyazomethine

Although apparently simple, the polycondensation reaction leading to polyazomethine is difficult to control because of its equilibrium character, the conversion degree being influenced by a series of parameters. The reaction between a siloxanediamine, 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane, and terephthalaldehyde was performed here in solution (in tetrahydrofuran) without by‐products removal and in absence of any catalyst or pH modifier. Different conditions (co‐monomers ratio, dilution, and temperature), considered as input parameters for the process modeling, were varied according to a pre‐established experimental program. The viscosity of the reaction mixture was chosen as output parameter, being monitored with a Haake Viscotester 7 Plus‐L. The process modeling was performed using a hybrid combination of artificial neural networks and differential evolution algorithm, the last one having the role of developing the neural model in an optimal form. The simulation results showed that the methodology provides accurate results, the model predictions being in close correlation with the experimental data. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42552.