Lubrication Mechanism of Phosphonium Phosphate Ionic Liquid Additive in Alkylborane–Imidazole Complexes

The assessment of ionic liquids (ILs) as lubricants in several tribological systems has shown their ability to provide remarkable reduced friction and protection against wear, whether they are used as additives or in the neat form. However, their corrosion and limited solubility in non-polar hydrocarbon oils represent the bottleneck-limiting factors for the use of ILs as lubricants. Therefore, in order to tackle these problems, mixtures of alkylborane–imidazole complexes with one halogen-free IL as additive were used in this study. The knowledge of the additive–surface interactions and hence the understanding of tribological properties are an important issue for lubricant formulations and were also investigated in this work. Thus, combination effects between two ionic liquid additives, a halogenated and a halogen-free one, were evaluated by a ball-on-disc-type tribometer under boundary lubrication conditions. Effective friction reduction and anti-wear properties have been demonstrated in tribological investigations when adding between 0.7 and 3.4 wt% of the halogen-free IL into base fluid composed of alkylborane–imidazole complexes. X-ray photoelectron spectroscopy analyses of the steel specimens were conducted to study the correlation between tribological properties and chemical surface composition of the boundary films formed on the rubbing surface. This work suggests potential applications for using halogen-free ILs as additives for synthetic ionic liquid lubricants.     

Cutting edge orthogonal contact-zone analysis using detailed tool shape representation

A new method for numerically controlled (NC)-simulation-based numerical analysis of the tool-workpiece contact area in cutting processes is presented. To gain enhanced knowledge about tool-workpiece interaction, determination of chip thickness, contact length, and resulting cross-section area of the undeformed chip is of major interest. Compared to common simulation approaches, where rotationally symmetrically constructed tool shape is used, the new method uses a detailed three-dimensional tool shape model for an extended and more accurate contact zone analysis. As a corresponding representation of the workpiece and its time-dependent change of shape, a multidexel model is used. To perform contact zone analysis, each cutting element and a multidexel model are intersected in discrete time steps corresponding to the tool rotation. Subsequently, the intersection point of each dexel is mapped on the local coordinate system of the cutting geometry. The parametric cutting geometry allows a direct computation of local cutting depth and contact length for each involved point. Based on the local values of contact length and cross section area of the undeformed chip, the characteristic values for the entire contact zone are calculated and used to predict mechanical loads caused by the cutting process. To demonstrate the application of the novel approach, a prediction of forces in slot milling and drilling of 1.1191 steel (C45EN) is presented.     

Advancement of an Interferometric Flow Velocity Measurement Technique by Adaptive Optics

Flow measurements often take place under difficult conditions. Optical flow measurement techniques are affected by variations of the refractive index, caused e.g., by temperature, concentration, or pressure gradients. This will give rise to an increased measurement uncertainty or cause the measurement to fail. To overcome these limitations, we propose the employment of adaptive optics. In this contribution we present interferometric flow velocity measurements through a fluctuating air-water interface by the use of adaptive optics. Using the adaptive optics, the rate of valid measurement signals can be improved from 28% to 83%. The results are promising to enable measurements in difficult environments affected by refractive index variations which were not accessible so far.     

Combined macro- and microrheometer for use with Langmuir monolayers

A Langmuir monolayer trough that is equipped for simultaneous microrheology and standard rheology measurements has been constructed. The central elements are the trough itself with a full range of optical tools accessing the air-water interface from below the trough and a portable knife-edge torsion pendulum that can access the interface from above. The ability to simultaneously measure the mechanical response of Langmuir monolayers on very different length scales is an important step for our understanding of the mechanical response of two-dimensional viscoelastic networks.     

Ultrafast thermal processing and nanocalorimetry at heating and cooling rates up to 1 MK/s

To generate artificial materials with advanced physical and chemical properties and to study phase transition kinetics on submillisecond time scale, an ultrafast nonadiabatic membrane nanocalorimeter was constructed. A set of commercially available membrane gauges for ultrafast nanocalorimetry has been developed. The gauges placed in a thermostat with controlled helium gas pressure and temperature can be utilized as devices for thermal processing and calorimetry with resolution of 1 nJ/K. Controlled ultrafast cooling, as well as heating, up to 10(6) K/s can be attained for nanogram samples. The maximum cooling rate is inversely proportional to the radius of the heated region of the gauge, which was in the range of 10-100 microm depending on the gauge. The minimum addenda heat capacity was 3 nJ/K. The dynamic heat-transfer problem for the temperature distribution in the membrane-gas system at ultrafast processing has been solved. The characteristic rate R(0) corresponding to quasistatic limit of the temperature change in the membrane-gas system has been found to be equal to 10(5) K/s for a 1 microm thick silicon nitride membrane in helium gas. Calorimeter performance at ultrafast rates has been verified by a set of test experiments. The method was applied for thermal processing and calorimetric measurements in a set of linear polymers. It has been established that nearly amorphous polyethylene can be obtained at a cooling rate of 10(6) K/s.     

Micro axial tomography: a miniaturized, versatile stage device to overcome resolution anisotropy in fluorescence light microscopy

With the development of novel fluorescence techniques, high resolution light microscopy has become a challenging technique for investigations of the three-dimensional (3D) micro-cosmos in cells and sub-cellular components. So far, all fluorescence microscopes applied for 3D imaging in biosciences show a spatially anisotropic point spread function resulting in an anisotropic optical resolution or point localization precision. To overcome this shortcoming, micro axial tomography was suggested which allows object tilting on the microscopic stage and leads to an improvement in localization precision and spatial resolution. Here, we present a miniaturized device which can be implemented in a motor driven microscope stage. The footprint of this device corresponds to a standard microscope slide. A special glass fiber can manually be adjusted in the object space of the microscope lens. A stepwise fiber rotation can be controlled by a miniaturized stepping motor incorporated into the device. By means of a special mounting device, test particles were fixed onto glass fibers, optically localized with high precision, and automatically rotated to obtain views from different perspective angles under which distances of corresponding pairs of objects were determined. From these angle dependent distance values, the real 3D distance was calculated with a precision in the ten nanometer range (corresponding here to an optical resolution of 10-30 nm) using standard microscopic equipment. As a proof of concept, the spindle apparatus of a mature mouse oocyte was imaged during metaphase II meiotic arrest under different perspectives. Only very few images registered under different rotation angles are sufficient for full 3D reconstruction. The results indicate the principal advantage of the micro axial tomography approach for many microscopic setups therein and also those of improved resolutions as obtained by high precision localization determination.     

High pressure cell for neutron reflectivity measurements up to 2500 bar

The design of a high pressure (HP) cell for neutron reflectivity experiments is described. The cell can be used to study solid-liquid interfaces under pressures up to 2500 bar (250 MPa). The sample interface is based on a thick silicon block with an area of about 14 cm(2). This area is in contact with the sample solution which has a volume of only 6 cm(3). The sample solution is separated from the pressure transmitting medium, water, by a thin flexible polymer membrane. In addition, the HP cell can be temperature-controlled by a water bath in the range 5-75°C. By using an aluminum alloy as window material, the assembled HP cell provides a neutron transmission as high as 41%. The maximum angle of incidence that can be used in reflectivity experiments is 7.5°. The large accessible pressure range and the low required volume of the sample solution make this HP cell highly suitable for studying pressure-induced structural changes of interfacial proteins, supported lipid membranes, and, in general, biomolecular systems that are available in small quantities, only. To illustrate the performance of the HP cell, we present neutron reflectivity data of a protein adsorbate under high pressure and a lipid film which undergoes several phase transitions upon pressurization.     

Investigation of long-term engine oil performance using lab-based artificial ageing illustrated by the impact of ethanol as fuel component

The effect of ethanol and its combustion products on the lubrication system is not very well understood. In this paper, a novel lab-based artificial ageing method for the evaluation of engine oils for bio-fuelled automotives and the results thereof are presented. Artificial ageing of three fully formulated engine oils with addition of ethanol, acetaldehyde, and acetic acid was carried out. The oil formulations chosen represent a consequent series of optimisation steps based on the engine oil performance in terms of preservation of typical oil parameters, e.g. base reserve and oxidation, observed during the artificial ageing procedure. It was shown that ethanol as well as acetaldehyde has almost no effect on the oil degradation especially in the case that advanced additive technology was used. On the contrary, acetic acid significantly affected the formulated oil showing influence on the detergent chemistry and even caused sludge formation. The use of the novel artificial ageing method proved to clearly differentiate the impact of the respective compounds added with the possibility to simulate enhanced stress conditions without the need of time-consuming and expensive engine bench tests. Hence, the novel setup offers valuable input for the formulation and the pre-selection of future engine oils suitable for bio-fuel.     

Silica gel supported zirconocene dichloride/methylalumoxane catalysts for ethylene polymerization: Effects of heterogenation on activity,polymer microstructure and product morphology

The system zirconocene dichloride/methylalumoxane was supported on silica in order to provide ethylene polymerization catalysts for suspension or gas phase processes. Highest activity was found for a sandwich-like, three layer anchoring of the zirconium centers on the support surface. The new catalyst systems show a decrease of activity compared to polymerization experiments in homogeneous phase. However, the molecular weights are increased and the weight distributions remain narrow by immobilization of the active catalyst sites. Those supported metallocene catalysts could find application for the synthesis of polyethylene materials with controlled rheology.     

Cycloadditions of 1-Aza-2-azoniaallene Salts derived from coumarin and camphor

The 1-aza-2-azoniaallene salt 8 prepared from 3-acetyl coumarin via the hydrazone 6 and the (chloroalkyl)azo derivative 7 reacts with nitriles to afford the 3-(3-chromenyl)-1,2,4-triazolium salts 11a–d . With diisopropylcarbodiimide the triazolium salt 13 and with norborene a tricyclic pyrazolium salt 14 are obtained. Concurrent to these cycloadditions the by-product 12 is formed by intramolecular cyclization of the cumulene 8 . Similarly, the intramolecular cyclization product 18 is isolated as the sole product when the 1-aza-2-azoniaallene salt 17a (prepared from the ethyl carbazone of camphor by chlorination and treatment of the product 16a with SbCl₅) was treated with nitriles, carbodiimides or alkenes. In contrast, 1,2,4-triazolium salts 20a–c , 23c , respectively pyrazolium salts 20d–f , and 1,3,4-thiadiazolium salts 23a,b are obtained by reaction of the 1-aza-2-azoniaallene salt 17b with nitriles, respectively alkenes, alkynes, diisopropylcarbodiimide, and isothiocyanates. The constitutions of two of these products ( 20e, 23a ) were secured by X-ray structural analysis.