Improving toughness of ultra-high molecular weight polyethylene with ionic liquid modified carbon nanofiber

Ionic liquids (ILs) with long alkyl substituted groups, including 1-docosanyl-3-methylimidazolium bromide (IL-1) and 1-docosanyl-3-methylimidazolium hexafluorophosphate (IL-2), were synthesized and used to modify the surface of carbon nanofibers (CNF). The nanocomposite film prepared by solution-blending of ionic liquid modified CNF (i-CNF) and ultrahigh molecular weight polyethylene (UHMWPE) displayed better toughness when compared with pure UHMWPE even at very low concentrations (e.g. 0.4 wt%). The effect of ionic liquids on the elongation-to-break ratio of this nanocomposite system was investigated. The ionic liquid with hexafluorophosphate as the anion was more efficient to increase the toughness of UHMWPE due to the improved compatibility of IL with UHMWPE in the polymer matrix than that of the bromide. The rheological behavior of molten nanocomposites revealed that the storage modulus and the complex viscosity decreased with increasing ionic liquid content in the high frequency region. However, a reverse trend was observed when the frequency was less than 0.05 s⁻¹. In-situ monitoring in the change of crystallinity of the nanocomposite during tensile deformation suggested a mechanism of sliding between UHMWPE crystal regions and the surface of carbon nanofibers.     

Endothelialization of Novel Magnesium-Rare Earth Alloys with Fluoride and Collagen Coating

Magnesium (Mg) alloys are promising scaffolds for the next generation of cardiovascular stents because of their better biocompatibility and biodegradation compared to traditional metals. However, insufficient mechanical strength and high degradation rate are still the two main limitations for Mg materials. Hydrofluoric acid (HF) treatment and collagen coating were used in this research to improve the endothelialization of two rare earth-based Mg alloys. Results demonstrated that a nanoporous film structure of fluoride with thickness of ~20 μm was formed on the Mg material surface, which improved the corrosion resistance. Primary human coronary artery endothelial cells (HCAECs) had much better attachment, spreading, growth and proliferation (the process of endothelialization) on HF-treated Mg materials compared to bare- or collagen-coated ones.     

On the tuning of predictive controllers: Impact of disturbances,constraints, and feedback structure

The impact of problem formulation modifications on predictive controller tuning is investigated. First, the proposed tuning method is shown to adapt to disturbance characteristic changes and thus, takes full economic advantage of the scenario. The second topic concerns point‐wise‐in‐time constraints and the impact of constraint infeasibility. Specifically, we shift the tuning question from selection of nonintuitive weighting matrix parameters to that of a few key parameters and results in a rather intuitive trade‐off between expected profit and expected constraint violations. Finally, we show that simple modifications will allow for the consideration of various feedback structures, including computational delay and partial state information. The overall conclusions of the work are that the results of the automated algorithm will help build an intuitive understating of the dynamics of the process and ultimately result in a higher level trade‐off between profit and constraint observance. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3473–3489, 2014     

Phase separation of a hafnium alkoxide-modified polysilazane upon polymer-to-ceramic transformation—A case study

The polymer-to-ceramic transformation of a hafnium alkoxide-modified polysilazane was investigated via thermogravimetric analysis coupled with in situ mass spectrometry (TG/MS), nuclear magnetic resonance (MAS NMR) and transmission electron microscopy (TEM). The results indicate that the structural evolution of the polysilazane upon ceramization is strongly affected by the modification with hafnium alkoxide. Thus, the content of carbon in the ceramic backbone was relatively low, whereas a large amount of SiN₄ sites and a segregated carbon phase was present in the sample. Furthermore, this study revealed the formation of a SiHfCNO amorphous single phase ceramic via pyrolysis of the polymer at 700 °C, whereas at higher pyrolysis temperatures precipitation of hafnia was observed, leading to an amorphous hafnia/silicon carbonitride ceramic nanocomposite. The precipitation of hafnia was shown to not rely on decomposition processes, but to be a result of rearrangement reactions occurring within the ceramic material.     

Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane

Titania-supported palladium catalysts modified by tungsten have been tested for the total oxidation of propane. The addition of tungsten significantly enhanced the catalytic activity. Highly active catalysts were prepared containing a low loading of 0.5 wt.% palladium, and activity increased as the tungsten loading was increased up to 6 wt.%. Catalysts were characterised using a variety of techniques, including powder X-ray diffraction, laser Raman spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and aberration-corrected scanning transmission electron microscopy. Highly dispersed palladium nanoparticles were present on the catalyst with and without the addition of WO_x. However, the addition of WO_x slightly increases the average palladium particle size, and there was some evidence for the Pd forming epitaxial islands on the support in the tungsten-doped samples. Surface analysis identified a combination of Pd⁰ and Pd²⁺ on a Pd/TiO₂ catalyst, whereas all of the Pd loading was found in the form of Pd²⁺ with the addition of tungsten into the catalysts. At low tungsten loadings, isolated monotungstate and some polytungstate species were highly dispersed over the titania support. The concentration of polytungstate species increased as the loading was increased, and it was also promoted by the presence of palladium. The coverage of the highly dispersed tungstate species over the titania also increased as the tungsten loading increased. Some tungstate species were also found to be associated with the palladium oxide particles, and there was an enrichment of oxidised tungsten species at the peripheral interface of the palladium oxide nanoparticles and the titania. Sub-ambient temperature–programmed reduction experiments identified an increased concentration of highly reactive species on catalysts with palladium and tungsten present together, and we propose that the new WO_x-decorated interface between PdO_x and TiO₂ particles may be responsible for the enhanced catalytic activity in the co-impregnated catalysts.     

Evaluation of Agronomic and Seed Characteristics in Elevated Oleic Acid Soybean Lines in the South-Eastern US

Increasing oleic acid, a monounsaturated fatty acid, is reported to strike the best balance between cold flow properties and oxidative stability in soybean seed oil to enhance biodiesel and produce a better burning fuel. In addition, it is important that elevated oleic acid soybeans have the agronomic traits of local cultivars and maintain oleic acid stability across environments. Research was conducted in 2007–2008 to evaluate six Roundup Ready^® soybean recombinant inbred lines exhibiting enhanced levels of oleic acid. The six elevated oleic lines averaged a 55% increase in oleic acid and a 43% decrease in linolenic acid over the two commercial cultivars (AG3906 and AG4103). Some elevated oleic acid genotypes fulfilled the linear regression definition of a stable genotype. TN03-93RR was the best genotype because of its oleic acid content (397 g kg^?1) and desirable regression estimates for stability. Iodine value (IV), peroxide value (PV), and induction period (IP) were used to evaluate the fuel properties of the two lines with the highest oleic acid content and the two commercial cultivars. The elevated oleic acid lines had significantly better IP, PV and IV for better biodiesel properties and oxidative stability than the two commercial cultivars.     

Manipulating crystal growth and polymorphism by confinement in nanoscale crystallization chambers

The phase behaviors of crystalline solids embedded within nanoporous matrices have been studied for decades. Classic nucleation theory conjectures that phase stability is determined by the balance between an unfavorable surface free energy and a stabilizing volume free energy. The size constraint imposed by nanometer-scale pores during crystallization results in large ratios of surface area to volume, which are reflected in crystal properties. For example, melting points and enthalpies of fusion of nanoscale crystals can differ drastically from their bulk scale counterparts. Moreover, confinement within nanoscale pores can dramatically influence crystallization pathways and crystal polymorphism, particularly when the pore dimensions are comparable to the critical size of an emerging nucleus. At this tipping point, the surface and volume free energies are in delicate balance and polymorph stability rankings may differ from bulk. Recent investigations have demonstrated that confined crystallization can be used to screen for and control polymorphism. In the food, pharmaceutical, explosive, and dye technological sectors, this understanding and control over polymorphism is critical both for function and for regulatory compliance. This Account reviews recent studies of the polymorphic and thermotropic properties of crystalline materials embedded in the nanometer-scale pores of porous glass powders and porous block-polymer-derived plastic monoliths. The embedded nanocrystals exhibit an array of phase behaviors, including the selective formation of metastable amorphous and crystalline phases, thermodynamic stabilization of normally metastable phases, size-dependent polymorphism, formation of new polymorphs, and shifts of thermotropic relationships between polymorphs. Size confinement also permits the measurement of thermotropic properties that cannot be measured in bulk materials using conventional methods. Well-aligned cylindrical pores of the polymer monoliths also allow determination and manipulation of nanocrystal orientation. In these systems, the constraints imposed by the pore walls result in a competition between crystal nuclei that favors those with the fastest growth direction aligned with the pore axis. Collectively, the examples described in this Account provide substantial insight into crystallization at a size scale that is difficult to realize by other means. Moreover, the behaviors resulting from nanoscopic confinement are remarkably consistent for a wide range of compounds, suggesting a reliable approach to studying the phase behaviors of compounds at the nanoscale. Newly emerging classes of porous materials promise expanded explorations of crystal growth under confinement and new routes to controlling crystallization outcomes.     

Experimental methods in chemical engineering: Electron paramagnetic resonance spectroscopy-EPR/ESR

Electron paramagnetic resonance (EPR) spectroscopy, also known as electron spin resonance spectroscopy (ESR), utilizes absorption of microwave radiation by unpaired electrons in a magnetic field. The interaction between the unpaired electron(s) and nearby magnetic nuclei helps identify paramagnetic species and can provide information about the motion of the molecule and the local polarity, pH, viscosity, concentration, and accessibility to other paramagnetic species. This mini-review discusses the fundamental underpinnings of EPR needed to correctly interpret EPR spectra. We describe various types of EPR spectra encountered by chemical engineers, and use application examples drawn from the chemical engineering literature to illustrate the information available from the technique. Few chemical engineering departments or even chemistry departments have EPR instruments, which contributes to the significant barrier that prevents this being adopted as a routine measurement technique. However, in 2016 and 2017, Web of Science indexed 7000 articles that applied EPR spectroscopy. A bibliometric map categorized the keywords in four categories based on co-occurrences: magnetic properties, films, and luminescence; crystal structure, complexes, and ligands; nanoparticles, oxidation, and degradation; and, systems, radicals, and H₂ O₂ .     

Synthesis and Structural Characterization of Macrocyclic Plasmin Inhibitors

Two series of macrocyclic plasmin inhibitors with a C-terminal benzylamine group were synthesized. The substitution of the N-terminal phenylsulfonyl group of a previously described inhibitor provided two analogues with sub-nanomolar inhibition constants. Both compounds possess a high selectivity against all other tested trypsin-like serine proteases. Furthermore, a new approach was used to selectively introduce asymmetric linker segments. Two of these compounds inhibit plasmin with K_i values close to 2 nM. For the first time, four crystal structures of these macrocyclic inhibitors could be determined in complex with a Ser195Ala microplasmin mutant. The macrocyclic core segment of the inhibitors binds to the open active site of plasmin without any steric hindrance. This binding mode is incompatible with other trypsin-like serine proteases containing a sterically demanding 99-hairpin loop. The crystal structures obtained experimentally explain the excellent selectivity of this inhibitor type as previously hypothesized.