Multicriteria optimization as enabler for Sustainable Ceramic Matrix Composites

Over the past 40 years, development of Ceramic Matrix Composites (CMCs) has focused mainly on the improvement of material performance and optimization of cost-efficient production routes. Recently, more fields of application have opened up for CMCs, in which environmental impacts are relevant. These impacts have barely been investigated so far but receive growing interest due to increasing awareness of the environmental consequences. Our innovative approach frames material properties in relation to environmental impacts (e.g., global warming potential in CO₂ emission) by varying process parameters to balance optimum performance against environmental considerations. First, the process of wet filament winding has been investigated up to the Carbon Fiber Reinforced Plastic (CFRP) state by changing both the curing and tempering temperatures. During the production of CFRP plates, mass and energy flows were tracked in each step. Three point-bending and interlaminar shear tests have been performed on the resulting samples to identify basic mechanical properties. The environmental impacts are determined by a cradle-to-gate Life Cycle Assessment (LCA), using the software SimaPro. The resulting tradeoffs between mechanical properties and environmental impacts show nonlinear behavior, thus revealing optimum points above which improved mechanical properties are associated with significantly higher CO₂ emissions.     

Minimizing profile error when estimating the sieve-size distribution of iron ore pellets using ordinal logistic regression

Size measurement of pellets in industry is usually performed by manual sampling and sieving techniques. Automatic on-line analysis of pellet size based on image analysis techniques would allow non-invasive, frequent and consistent measurement. We evaluate the statistical significance of the ability of commonly used size and shape measurement methods to discriminate among different sieve-size classes using multivariate techniques. Literature review indicates that earlier works did not perform this analysis and selected a sizing method without evaluating its statistical significance. Backward elimination and forward selection of features are used to select two feature sets that are statistically significant for discriminating among different sieve-size classes of pellets. The diameter of a circle of equivalent area is shown to be the most effective feature based on the forward selection strategy, but an unexpected five-feature classifier is the result using the backward elimination strategy. The discrepancy between the two selected feature sets can be explained by how the selection procedures calculate a feature's significance and that the property of the 3D data provides an orientational bias that favours combination of Feret-box measurements. Size estimates of the surface of a pellet pile using the two feature sets show that the estimated sieve-size distribution follows the known sieve-size distribution.     

Supramolecular Capsules Derived from Resorcin[4]arenes by H-Bonding and Metal Coordination: Synthesis,Characterization, and Single-Molecule Force Spectroscopy

Self-assembly by H-bonding and by metal-coordination of functionalized calix[4]arenes and cavitands to large supramolecular capsules is described. In addition, a new method of analyzing supramolecular recognition processes at the single molecule level is discussed. By measuring interaction forces in a hydrogen-bonded assembly using single-molecule force spectroscopy (SMFS), the dynamics of the self-assembly process can be evaluated. In the future, consequent application of this new technique will influence supramolecular design principles and the use of non-covalent interactions as construction elements in the field of nanotechnology.     

Hydrogen sensor based on a graphene – palladium nanocomposite

A composite material was prepared from graphene and palladium nanoparticles (PdNP) by layer-by-layer deposition on gold electrodes. The material was characterized by absorption spectroscopy, scanning electron microscopy, Raman spectroscopy and surface plasmon resonance. Cyclic voltammetry demonstrated the presence of electrocatalytic centers in the palladium decorated graphene. This material can serve as a sensor material for hydrogen at levels from 0.5 to 1% in synthetic air. Pure graphene is poorly sensitive to hydrogen, but incorporation of PdNPs increases its sensitivity by more than an order of magnitude. The effects of hydrogen, nitrogen dioxide and humidity were studied. Sensor regeneration is accelerated in humid air. The sensitivity of the nanocomposite depends on the number of bilayers of graphene–PdNPs.     

Experimental Validation of a Fundamental Model for PCR Efficiency

Recently a theoretical analysis of PCR efficiency has been published by Booth et al. (2010). The PCR yield is the product of three efficiencies: (i) the annealing efficiency is the fraction of templates that form binary complexes with primers during annealing, (ii) the polymerase binding efficiency is the fraction of binary complexes that bind to polymerase to form ternary complexes and (iii) the elongation efficiency is the fraction of ternary complexes that extend fully. Yield is controlled by the smallest of the three efficiencies and control could shift from one type of efficiency to another over the course of a PCR experiment. Experiments have been designed that are specifically controlled by each one of the efficiencies and the results are consistent with the mathematical model. The experimental data has also been used to quantify six key parameters of the theoretical model. An important application of the fully characterized model is to calculate initial template concentration from real-time PCR data. Given the PCR protocol, the midpoint cycle number (where the template concentration is half that of the final concentration) can be theoretically determined and graphed for a variety of initial DNA concentrations. Real-time results can be used to calculate the midpoint cycle number and consequently the initial DNA concentration, using this graph. The application becomes particularly simple if a conservative PCR protocol is followed where only the annealing efficiency is controlling.     

Lipoxygenase Products in the Urine Correlate with Renal Function and Body Temperature but not with Acute Transplant Rejection

Acute transplant rejection is the leading cause of graft loss in the first months after kidney transplantation. Lipoxygenase products mediate pro- and anti-inflammatory actions and thus we aimed to correlate the histological reports of renal transplant biopsies with urinary lipoxygenase products concentrations to evaluate their role as a diagnostic marker. This study included a total of 34 kidney transplant recipients: 17 with an acute transplant rejection and 17 controls. LTE4, LTB4, 12-HETE and 15-HETE concentrations were measured by enzyme immunoassay. Urinary lipoxygenase product concentrations were not significantly changed during an acute allograft rejection. Nevertheless, LTB4 concentrations correlated significantly with the body temperature (P ≤ 0.05) 3 months after transplantation, and 12- and 15-HETE concentrations correlated significantly with renal function (P ≤ 0.05) 2 weeks after transplantation. In conclusion, our data show a correlation for LTB4 with the body temperature 3 months after transplantation and urinary 12- and 15-HETE concentrations correlate positively with elevated serum creatinine concentrations but do not predict acute allograft rejection.     

N-methyl-2-hydroxyethylammonium oleate ionic liquid performance as corrosion inhibitor for mild steel in hydrochloric acid medium

The aim of the present study is to evaluate the performance of N-methyl-2-hydroxyethylammonium oleate ([m-2HEA][Ol]) as a corrosion inhibitor for mild steel in a 0.1-mol/L hydrochloric acid solution and also investigate the role of chloride in the inhibition mechanism. This protic ionic liquid (PIL) has formerly shown a high efficiency as a corrosion inhibitor in a neutral chloride medium. Electrochemical and weight loss measurements, surface contact angle determination, scanning electron microscopy, and Raman spectroscopy were used to understand the factors that influence the response of the studied inhibitor. Results revealed that [m-2HEA][Ol] behaves as a mixed-type adsorption inhibitor, by blocking cathodic sites and by modifying the activation energy of the anodic reaction, and it can reach up to 94–97% of inhibition efficiency. PIL adsorption was enhanced by the excess of positive charge of the mild steel. The effect of inhibitor molecule has been discussed to propose a mechanism that explains the inhibitory action of the corrosion inhibitor, pointing out the role of chloride in the inhibition mechanism.     

Cyclohexa‐3,5‐diene‐1,2‐trans‐diols – Synthesis and Application in Target‐Oriented Syntheses

An exhaustive overview of the field of cyclohexa‐3,5‐diene‐1,2‐trans‐diols is given. Early and recent methods for the formation of the compounds are reviewed and the various syntheses in which the title compounds have been applied are presented. Special emphasis is given to naturally occurring epoxides, which have been the dominant target molecules since the 1970s. Finally, recent advances in biotechnology are highlighted; with the increased availability of the enantiomerically pure cyclohexa‐3,5‐diene‐1,2‐trans‐diols, new synthetic endeavours were initiated.     

Contribution of the Internal and External Oxygen to the Oxidation of Microencapsulated Fish Oil

Microencapsulation aims to protect polyunsaturated fatty acids against oxidation by embedding oil droplets in a solid matrix. In such a system the internal (dissolved and entrapped) and external (in the environment) oxygen can be differentiated. The study aims to quantify the impact of both oxygen sources on the oxidation of microencapsulated fish oil. The impact of the solubilized oxygen in bulk fish oil is investigated by saturating the oil with nitrogen, synthetic air, and pure oxygen. Even though more dissolved oxygen results in more oxidation products, the difference between the oxidation of the nitrogen and air saturated oil is significant but low. For encapsulated fish oil powders, the internal oxygen is modified by preparing oil‐in‐water emulsions under atmospheric and inert conditions. The feed is atomized and spray dried with either nitrogen or air. Powders are stored under vacuum and in vials and the hydroperoxides and anisidine value are determined in the total‐ and encapsulated oil. The internal oxygen has a minor impact, whereas the external oxygen is the main determinant for autoxidation. Apart from oxidizing the non‐encapsulated oil, the external O₂ penetrates into the particle and reacts with the encapsulated oil. Practical Applications: Comparing the contribution of the internal and external oxygen to the oxidative stability shows that the internal O₂ plays a minor role and can be neglected. This means that the emulsion preparation as well as the spray drying process can be conducted under ambient conditions. An inert production is not extending the shelf life significantly as long as the external O₂ determines oxidation. The focus should be on optimizing the diffusion barrier properties of the wall matrix to reduce the penetration of the external oxygen into the particle system. Alternatively, packaging solution reducing the external O₂ will extend the shelf life of the microencapsulated oil.     

Deliberately Losing Control of C−H Activation Processes in the Design of Small-Molecule-Fragment Arrays Targeting Peroxisomal Metabolism

Combined photochemical arylation, “nuisance effect” (S_NAr) reaction sequences have been employed in the design of small arrays for immediate deployment in medium-throughput X-ray protein–ligand structure determination. Reactions were deliberately allowed to run “out of control” in terms of selectivity; for example the ortho-arylation of 2-phenylpyridine gave five products resulting from mono- and bisarylations combined with S_NAr processes. As a result, a number of crystallographic hits against NUDT7, a key peroxisomal CoA ester hydrolase, have been identified.