Experimental simulation of chemical reactions between ZDDP tribofilms and steel surfaces during friction processes

Friction tests are performed in a controlled environment (Ultra High Vacuum), between steel surfaces and a ZDDP tribofilm at different contact severities. According to AES analyses, evidence of chemical reactions activated by friction is given. The reaction of the ZDDP tribofilm with the native iron oxide could partially explain its antiwear behavior.     

Structural Changes in Tribo-Stressed Zinc Polyphosphates

The influences of pressure, shear stress and temperature on the structure of zinc orthophosphate and zinc metaphosphate was investigated. Tribological tests were performed to study the combined effect of pressure and shear stress at two temperatures. Friction tests were carried out in the boundary lubrication regime from dispersions of zinc polyphosphates in base oil. The effects of pressure alone were investigated using a diamond anvil cell in order to separate it from those of shearing. Raman spectroscopy was used to follow in situ or ex situ the structural changes of the zinc polyphosphate powders and the tribo-stressed areas. Tribofilms obtained with both polyphosphates display a partial and full depolymerization of the zinc metaphosphate at ambient and high (120 °C) temperature, respectively. The large stress and strain conditions of the tribological tests are necessary to induce a tribochemical reaction between zinc metaphosphate and iron oxide leading to a depolymerization of the phosphate in the tribofilm. The tribochemical reaction and antiwear tribofilm formation are significantly enhanced by the modest temperature increase from ambient to 120 °C. Pressure alone induces only disordering in the structure of zinc polyphosphates, with only minor changes of the chain length in phosphates and does not contribute significantly to the observed structural changes in tribofilms.     

In situ analysis of bismuth telluride electrodeposition using combined spectroscopic ellipsometry and electrochemical quartz crystal microbalance

Electrodeposition of bismuth telluride (Bi₂Te₃) in an acidic medium with Arabic gum by galvanostatic polarization has been investigated. Simultaneous in situ spectroscopic ellipsometry and gravimetric measurements have been performed to study the morphological evolution of the compound. A progressive covering stage was demonstrated and revealed that a 40 nm thick film has already acquired morphological and optical behavior similar to that of thicker films. The optical thickness and electrochemical quartz crystal microbalance (EQCM) mass are coherent with a density of 7.06. Combined gravimetric and coulometric data confirm the formation of Bi₂Te₃ by determining the ratio m/z.     

Pulsed electrodeposition of (Bi1-xSbx)2Te3 thermoelectric thin films

(Bi_1-xSb_x)₂Te₃ thermoelectric thin films were deposited on stainless steel discs in 1 M perchloric acid and 0.1 M tartaric acid by pulse electrodeposition in order to optimize the grain growth. The influence of the electrolyte composition, the cathodic current density and the cathodic pulse time on film stoichiometry were studied. The results show that it is necessary to increase the Sb content in the electrolyte to obtain the (Bi_0.25Sb_0.75)₂Te₃ film stoichiometry. Pulse plating reduced the grain size and the roughness, compared with continuous plating. Thermoelectric and electrical properties were also studied and it was found that the Seebeck coefficient and electrical resistivity were related to two parameters: the cathodic pulse current density and the films thickness.     

Control of heat transfer and growth uniformity of solidifying copper shells through substrate temperature

To determine the optimal roll temperature in a twin-roll copper-strip caster, copper blocks preheated between 25 °C and 350 °C were immersed in a bath of molten copper for 0.5 seconds. A significant increase in the contact heat-transfer coefficient at the substrate-shell interface was obtained when the substrates were heated above 200 °C and the gain in the solidified shell thickness was 20 pct. The shell growth was also approximately 35 pct more uniform at a high substrate temperature, and micrographic examination showed the dendritic structure to be finer. The contact heat-transfer coefficient was decomposed into two constituents, one for the substrate and the other for the shell. The former was found to be the limiting factor in heat transfer.     

Ecological risk assessment of urban and industrial systems: a review

Numerous ecological risk assessment methodologies have been developed over the last twenty years around the world for evaluating urban and industrial systems and installations, by both the organisations responsible for implementing regulations and the scientific community. Although these methodologies share the general principle underlying their use, they differ widely with respect to the approaches chosen and the resources employed to apply them. Also, they may even have different objectives: prior assessment as part of an impact study before building a new installation, or retrospective assessment, for example, in view to explaining the reasons for an impact recorded or for forecasting additional expected impacts.This article provides a synthesis of the different approaches used around the world for carrying out each of the major steps common to all ecological risk assessment methodologies. The advantages and limitations of these different options are discussed in order to provide elements for formulating any new methodology adapted to a given scenario. To conclude, perspectives for improving the tools required for these methodologies are proposed, and the research works to which priority should be given are identified.     

Development of biodegradable polymeric nanoparticles for encapsulation,delivery, and improved antifungal performance of natamycin

The aim of this study was to evaluate biodegradable poly(lactide‐co‐glycolide) nanoparticles as potential nano‐delivery systems for the food antifungal compound natamycin. Natamycin‐loaded nanoparticles were prepared at various ratios polymer/antifungal by the nanoprecipitation technique, resulting in nano‐size particles (80–120 nm) with a narrow distribution and a spherical morphology. Complexation of natamycin with PLGA and active participation to the nanoparticle formation were evidenced by a mean diameter reduction of 10–30 nm, although encapsulation levels remained low due to the zwitterionic and partially hydrophilic nature of natamycin. Physical state analyses highlighted the presence of natamycin in an amorphous or molecularly dispersed state within the polymeric matrix. This translates into high availability of free antifungal molecules reflected in burst release and fast in vitro release kinetics rates as well as enhanced antifungal performance against the model food yeast Saccharomyces cerevisiae, offering a potential benefit for antifungal protection compared with the commercially available natamycin products. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43736.     

Antiwear Chemistry of ZDDP: Coupling Classical MD and Tight-Binding Quantum Chemical MD Methods (TB-QCMD)

Zinc dialkyl dithiophosphate (ZDDP) is an antiwear additive for steel surfaces currently used in most of engine oils. The mechanism by which the additive is active is based on tribochemical reactions. These reactions occur in the contact zone under the combined effects of pressure and shear. These reactions are predictable on the basis of the HSAB principle (or Chemical Hardness model). We show here that computer simulations can describe the reactions much more accurately than the HSAB principle thanks to the use of a hybrid technique, coupling classical MD and tight-binding quantum chemical MD. In this study, we focused on one of the basic tribochemical reactions of ZDDP: the ability of zinc polyphosphate to react with abrasive metal oxides nanoparticles under pressure and shear. Results show that the driving forces for the reaction are mainly the increases of molecular shearing and entropy, besides temperature. We also studied the case of other metal oxide particles that emanate from elements of addition in steel compositions. We show that manganese and chromium oxides are eliminated in the same way as iron oxides, being in agreement with experimental data obtained by X-ray microanalysis and FIB-TEM characterizations. Eventually, we investigated the case of Al/Si alloys and showed that alumina particles can hardly be digested by zinc phosphate, at the opposite of silica particles. This explains very well why ZDDP is not a good antiwear additive for aluminium alloys and why the presence of silicon grain in the alloy is favourable.