Characterization of Oleogels Based on Waxes and Their Hydrolyzates

In this paper, the structuring of liquid oils, also known as oleogelation, is systematically investigated for the first time using a quasi-quaternary mixing system approach. Native waxes with different quantities of wax esters (WE), n-alkanes (hydrocarbons (HC)), fatty acids (FA), and fatty alcohols (FaOH) are applied in mixtures with hydrolyzed waxes to systematically change the composition. Hydrolyzed waxes contain high levels of FA and FaOH. The model systems are investigated on microscopic level (brightfield light microscopy (BFM), cryogenic scanning electron microscopy (cryo-SEM)) as well as on their macroscopic properties (rheology, gel hardness) and calorimetric behavior (differential scanning calorimetry (DSC)). It is found that sunflower wax (SFW)-based gels (12% structurant) become less hard on any admixture. Beeswax (BW)-based gels show significant increases in hardness when 25% and 50% (w/w) hydrolyzate are admixed. This could be related to stepwise crystallization. Further analysis reveals that the dissolution/melting behavior of the wax ester mixtures can be surprisingly well described as ideal solubility of a single pseudocomponent. The approach to unravel the individual contributions of the different species present in waxes is successful and marks a first step to better understand the systematic of wax functionality as oleogelators. Practical Application: The substitution of hardstock fats in structured oil phases is of interest for two reasons. The improved nutritional profile oleogels offer are beneficial for public health while the elimination of palm oil based ingredients appears to be a general public desire. Among the technical solutions for non-TAG oil structuring waxes are very promising. This is primarily due to their availability, prior consumption, potentially low cost for functionality. Currently waxes are technically and scientifically wrongly treated as single components. In order to better utilize the potential of waxes and design future sourcing strategies it is necessary to understand the wax functionality at a compositional/molecular level. This contribution marks the first step into this direction by considering classes of molecules with respect to their contribution to functionality. This understanding is considered as a key for future compositional design.     

Effective Formal Reduction of Linear Differential Systems

In this paper we present a new method for the formal reduction of linear differential systems. We generalize classical results and concepts and obtain new characterizations of existing notions. Our main result is a generalization of the classical Splitting Lemma. This leads to an algorithm for computing formal invariants and solutions in a more efficient way. Received: March 9, 1999; revised version: September 2, 1999     

Modeling of a semi-hermetic CO2 reciprocating compressor including lubrication submodels for piston rings and bearings

A comprehensive model for a semi-hermetic CO₂ reciprocating compressor is presented. This comprehensive model is composed of three main sub-models simulating the geometry and kinematics, the compression process, and frictional power loss. Valve and leakage sub-models are included in the compression process model. The frictional power loss model includes the friction at the bearings and between the piston ring and cylinder wall. The predicted results of the comprehensive model are validated using external compressor performance measurements of compressor input power and mass flow rate. The mass flow rate and compressor input power are predicted to within 4.03% and 6.43% mean absolute error, respectively, compared to the experimental datum. Additionally, a parametric study is presented which investigates compressor performance as a function of the stroke-to-bore ratio.     

Preparation of Ring-Shaped Thermoelectric Legs from PbTe Powders for Tubular Thermoelectric Modules

Waste heat recovery—for example, in automotive applications—is a major field for thermoelectric research and future application. Commercially available thermoelectric modules are based on planar structures, whereas tubular modules may have advantages for integration and performance in the field of automotive waste heat recovery. One major drawback of tubular generator designs is the necessity for ring-shaped legs made from thermoelectric material. Cutting these geometries from sintered tablets leads to considerable loss of thermoelectric material and therefore high cost. Direct sintering of ring-shaped legs or tubes of thermoelectric material is a solution to this problem. However, sintering such rings with high homogeneity and density faces some difficulties related to the mechanical properties of typical thermoelectric materials such as lead telluride (PbTe)—particularly brittleness and high coefficient of thermal expansion. This work shows a process for production of thermoelectric rings made of p- and n-doped PbTe. Long tubes of PbTe have been sintered in a current-assisted sintering process with specially designed sintering molds, coated with a diffusion barrier, and finally cut into ring-shaped slices. To demonstrate the technology, a tubular thermoelectric module has been assembled using these PbTe rings.     

Localised visualisation of O2 consumption and H2O2 formation by means of SECM for the characterisation of fuel cell catalyst activity

Catalytic reduction of O₂ at metal catalysts either follows a 2-electron transfer pathway to the formation of H₂O₂ or a 4-electron transfer pathway to the formation of H₂O. The branching ratio of this reaction has a significant impact on the applicability of catalyst materials. The previously introduced oxygen competition mode of SECM, which allows high-resolution imaging of local O₂ consumption, has been extended to a potential-pulse sequence enabling the sequential detection of O₂ reduction followed by the detection of local H₂O₂ formation. Thus, not only the local catalytic activity of a catalyst can be visualised but, additionally, the degree of the branching can be estimated. The selectivity of a catalyst candidate can thereby be visualised sequentially to the elucidation of its activity. First results on the properties of electrodeposited Pt and Au test structures are shown demonstrating the feasibility to clearly distinguish catalyst activity and selectivity under variation of the polarisation potential.     

Textile solar light collectors based on models for polar bear hair

Concepts of technical fibers following models for the polar bear hair to be used for textile solar collectors are discussed. The approach to coat fibers with a thin layer into which fluorescent dyestuff was dispersed was studied experimentally. Modified fibers made of different polymers were characterized with respect to optical properties relevant for the bionic model. In the case of poly(methylmethacrylate) fibers, the envisaged effect could be achieved to high efficiency. The optical performance could be enhanced by ultrasonic dispersion of the dyestuff in the coating matrix. The effect is less significant in semi-crystalline fibers such as poly(ethylene terephthalate), which is attributed to diffuse scattering.     

The fabrication of nanoporous Pt-based multimetallic alloy nanowires and their improved electrochemical durability

A general approach for the fabrication of nanoporous Pt-based multimetallic alloy nanowires is reported, which involves electrodeposition of corresponding precursor alloys into porous anodic alumina templates, followed by a mild dealloying process. Nanoporous ternary PtCoNi and PtCoAu as well as quaternary PtRuCoNi nanowires were successfully fabricated, and their microstructure and composition were examined by transmission electron microscopy. Electrochemical tests showed that these porous nanowires exhibit higher electrochemically active surface area and much improved durability compared to commercially available Pt black, and may find potential applications in electrocatalysis and electrochemical sensing.     

An Alternative Route Towards Metal–Polymer Hybrid Materials Prepared by Vapor‐Phase Processing

Transition metals incorporated into polymers lead to unusual or improved physical properties that significantly differ from those of purely organic polymers. A simple and practicable incorporation of diverse transition metals into any available polymer would make an important contribution to overcome some of the synthetic difficulties of metal‐polymer hybrid materials. Here, it is demonstrated that atomic layer deposition (ALD) can be a promising means to resolve some of those difficulties. It is found that even polytetrafluoroethylene (PTFE) with its great physical and chemical stability can be easily transformed into a transition metal–PTFE hybrid material simply by applying a metal‐oxide ALD process to PTFE. Upon metal incorporation into the PTFE, the molecular structure as well as mechanical properties (tensile behavior) of PTFE were observed to significantly change. For a better understanding of the changes to the material, experimental investigations using Raman spectroscopy, attenuated‐total‐reflection Fourier‐transform infrared spectroscopy, wide‐angle X‐ray diffraction, and energy‐dispersive X‐ray analysis were performed. In addition, with density functional theory calculations, potential bonding states of the incorporated metal into PTFE were modeled and predicted. The ALD‐based vapor‐phase approach for metal incorporation into a polymer could bring about rapid progress in the research area of metal–polymer hybrid materials.