Mixed Lubrication with C18 Fatty Acids: Effect of Unsaturation

In this paper, the lubrication mechanism of fatty acids is revisited with a new approach combining experimental and computational chemistry studies. The lubricating properties of single and mixtures of stearic, oleic and linoleic acids in a synthetic Poly-Alpha-Olefin base oil (PAO4) on iron oxide surface are investigated under mixed boundary regime with temperatures from 50 °C up to 150 °C. Low friction coefficient (about 0.055) with no visible wear is reported in the presence of single stearic acid at high temperature. This lubricating behavior is inhibited in the presence of unsaturated fatty acids highlighting an anti-synergic effect of a saturated/unsaturated mixture, especially at 150 °C. To understand the anti-synergic effect and the adsorption mechanism of these molecules, molecular dynamic (MD) and quantum chemistry simulations are performed to evaluate their diffusion coefficient in PAO4 and their adsorption mechanism on iron oxide at different temperatures. MD simulation results show a faster diffusion toward the surface for unsaturated fatty acids than for saturated fatty acid at all the studied temperatures. This means that unsaturated molecules arrive and mainly adsorb before stearic acid on the surface leading to a tribological behavior of the mixture characteristic of the unsaturated molecule. Computational chemistry suggests that all fatty acids (saturated and unsaturated) adsorption mechanism is due to the chemisorption of the carboxylic group on iron oxide surface with no desorption up to 150 °C.     

Zinc Dialkyl Phosphate (<Emphasis Type=Bold>ZP</Emphasis>) as an Anti-Wear Additive: Comparison with <Emphasis Type=Bold>ZDDP</Emphasis>

In this study, we are interested in the anti-wear properties of zinc dialkyl phosphate additive (ZP) in comparison with ‘classical’ zinc dialkyldithiophosphate (ZDDP). Friction tests were performed on a reciprocating tribometer using both ball-on-flat and cylinder-on-flat configurations under a Hertzian contact pressure of 0.9 GPa. Experiments were carried out as a function of temperature (25 and 100 °C), sliding speed (25, 50 and 100 mm/s) and additives concentrations. Ball wear scar diameters as well as friction coefficient were measured. In order to better understand the anti-wear mechanisms of these additives, friction tests were followed by surface analyses such as AES (Auger Electron Spectroscopy) and XPS (X-Ray Photoelectron Spectroscopy). Transmission Electron Microscopy (TEM) observations of the ZDDP and ZP tribofilms were also carried out to visualise the generated layers. The anti-wear capability of ZP molecule is discussed.     

On-line 3-D system for the inspection of deformable parts

In spite of the development of automated tolerance inspection systems for manufactured parts over the years, there are still processes that inevitably require manual intervention making full automation impossible in most cases; in particular when dealing with deformable parts. In most current industrial inspection systems, a deformable part under inspection must first be mechanically constrained on a rigid support or jig so as to be able to compare it with its nominal shape. This paper presents a new system to perform real-time surface inspection of deformable parts that does not require fixturing. Instead, the proposed system applies virtual forces to the part??s CAD model as if the part was installed in the fixturing device. Normally, a precise finite element method (FEM) simulation should be used to approximate the deformation that appends when the part is installed in the device. Even with a fast parallel computer, FEM is far from being real-time and cannot be used for on-line inspection. In the proposed system, a radial basis function approximation of the FEM simulation is trained off-line and used to speed-up the simulation by an order of magnitude. Experimental evaluation of the proposed system is presented for three plastic parts. Using the proposed scheme, an approximation of 0.25?mm compared with the real deformation was obtained. In this paper, statistical results are presented such as the average deviation, standard deviation, and processing time between the approximations obtained with the proposed method and with the finite element method applied to the full CAD model.     

Metal transfer to plants grown on a dredged sediment: use of radioactive isotope 203Hg and titanium

Improperly disposed of dredged sediments contaminated with metals may induce long-term leaching and an increase of metal concentrations in ground waters and vegetal cover plants. The objective of the study was to quantify the sediment-to-plant transfer of Cu, Pb, Hg and Zn with a particular focus on the pathway of Hg and to determine whether the establishment of vegetal cover modifies the metal availability. A pot experiment with rape (Brassica napus), cabbage (Brassica oleraccea) and red fescue (Festuca rubra) was set up using a sediment first spiked with the radioisotope 203Hg. Zinc concentrations (197-543 mg kg(-1) DM) in leaves were higher than Cu concentration (197-543 mg kg(-1) DM), Pb concentration (2.3-2.6 mg kg(-1) DM) and Hg concentration (0.9-1.7 mg kg(-1) DM). Leaves-to-sediment ratios decreased as follows: Zn > Cu > Hg > Pb. According to Ti measurements, metal contamination by dry deposition was less than 1%. Mercury concentration in plant leaves was higher than European and French thresholds. Foliar absorption of volatile Hg was a major pathway for Hg contamination with a root absorption of Hg higher in rape than in cabbage and red fescue. Growth of each species increased Cu solubility. Zinc solubility was increased only in the presence of rape. The highest increase of Cu solubility was observed for red fescue whereas this species largely decreased Zn solubility. Dissolved organic carbon (DOC) measurements suggested that Cu solubilisation could result from organic matter or release of natural plant exudates. Dissolved inorganic carbon (DIC) measures suggested that the high Zn solubility in the presence of rape could originate from a generation of acidity in rape rhizosphere and a subsequent dissolution of calcium carbonates. Consequently, emission of volatile Hg from contaminated dredged sediments and also the potential increase of metal solubility by a vegetal cover of grass when used in phytostabilisation must be taken into account by decision makers.     

Optical constants of electroplated Bi2Te3 films by Mueller matrix spectroscopic ellipsometry

We synthesized polycrystalline Bi_2 + xTe_3 − x (− 0.2< x <0.2) thin films by electrodeposition in acidic medium. Since Bi₂Te₃-like structure may be uniaxially anisotropic due to its rhombohedral crystallographic system, we investigated their optical behavior using ex and in situ Mueller matrix spectroscopic ellipsometry in the wavelength range of 470 to 830 nm (1.5-2.6 eV). We found that room-temperature electroplated polycrystalline appears optically isotropic and that no depolarization effect occurs from the first steps of growth until several micrometers thick films. Additional ex situ measurements permit to obtain their optical constants from far-ultraviolet to near-infrared (190-2100 nm).     

Radio‐opaque fecal impaction and pseudo‐occlusion in a dialyzed patient taking lanthanum carbonate

Lanthanum therapy is an efficient therapy of hyperphosphoremia by chelating phosphore in the digestive tract. Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table. This drug is lightly absorbed and has low water solubility. It should be borne in mind that abdominal X‐rays of patients taking lanthanum carbonate may have a radio‐opaque appearance typical of imaging agents. This characteristic is suggested to confirm adherence of the patient by doing an abdominal X‐ray. We describe in our case a particular good compliant patient with slow digestive transit, which ends by pseudo‐occlusion.     

Quality by design compliant analytical method validation

The concept of quality by design (QbD) has recently been adopted for the development of pharmaceutical processes to ensure a predefined product quality. Focus on applying the QbD concept to analytical methods has increased as it is fully integrated within pharmaceutical processes and especially in the process control strategy. In addition, there is the need to switch from the traditional checklist implementation of method validation requirements to a method validation approach that should provide a high level of assurance of method reliability in order to adequately measure the critical quality attributes (CQAs) of the drug product. The intended purpose of analytical methods is directly related to the final decision that will be made with the results generated by these methods under study. The final aim for quantitative impurity assays is to correctly declare a substance or a product as compliant with respect to the corresponding product specifications. For content assays, the aim is similar: making the correct decision about product compliance with respect to their specification limits. It is for these reasons that the fitness of these methods should be defined, as they are key elements of the analytical target profile (ATP). Therefore, validation criteria, corresponding acceptance limits, and method validation decision approaches should be settled in accordance with the final use of these analytical procedures. This work proposes a general methodology to achieve this in order to align method validation within the QbD framework and philosophy. β-Expectation tolerance intervals are implemented to decide about the validity of analytical methods. The proposed methodology is also applied to the validation of analytical procedures dedicated to the quantification of impurities or active product ingredients (API) in drug substances or drug products, and its applicability is illustrated with two case studies.     

Solid lipid nanoparticles incorporating melatonin as new model for sustained oral and transdermal delivery systems

melatonin (MT) is a hormone produced by the pineal gland at night, involved in the regulation of circadian rhythms. For clinical purposes, exogenous MT administration should mimic the typical nocturnal endogenous MT levels, but its pharmacokinetics is not favourable due to short half-life of elimination. Aim of this study is to examine pharmacokinetics of MT incorporated in solid lipid nanoparticles (SLN), administered by oral and transdermal route. SLN peculiarity consists in the possibility of acting as a reservoir, permitting a constant and prolonged release of the drugs included. In 7 healthy subjects SLN incorporating MT 3 mg (MT-SLN-O) were orally administered at 8.30 a.m. MT 3 mg in standard formulation (MT-S) was then administered to the same subjects after one week at 8.30 a.m. as controls. In 10 healthy subjects SLN incorporating MT were administered transdermally (MT-SLN-TD) by the application of a patch at 8.30 a.m. for 24 hours. Compared to MT-S, Tmax after MT-SLN-O administration resulted delayed of about 20 minutes, while mean AUC and mean half life of elimination was significantly higher (respectively 169944.7 +/- 64954.4 pg/ml x hour vs. 85148.4 +/- 50642.6 pg/ml x hour, p = 0.018 and 93.1 +/- 37.1 min vs. 48.2 +/- 8.9 min, p = 0.009). MT absorption and elimination after MT-SLN-TD demonstrated to be slow (mean half life of absorption: 5.3 +/- 1.3 hours; mean half life of elimination: 24.6 +/- 12.0 hours), so MT plasma levels above 50 pg/ml were maintained for at least 24 hours. This study demonstrates a significant absorption of MT incorporated in SLN, with detectable plasma level achieved for several hours in particular after transdermal administration. As dosages and concentrations of drugs included in SLN can be varied, different plasma level profile could be obtained, so disclosing new possibilities for sustained delivery systems.     

Long-term outcomes in open pelvic fractures

BACKGROUND: Open pelvic fractures represent one of the most devastating injuries in orthopedic trauma. The purpose of this study was to document the injury characteristics, complications, mortality, and long-term, health-related quality of life outcomes in patients with open pelvic fractures. METHODS: The trauma registry at an adult trauma center was used to identify all multiple system blunt trauma patients with a pelvic fracture from January of 1987 to August of 1995 (n = 1,179). Demographic data, mechanism of injury, and fracture type were determined from hospital records. Short-term outcome measures included infectious complications, mortality, and length of stay in hospital. Long-term outcomes of survivors were obtained by telephone interview using the SF-36 Health Survey and the Functional Independence Measure. RESULTS: Open pelvic fractures were uncommon, occurring in 44 patients (4%). Patients with open fractures were about 9 years younger, on average, than patients with closed fractures (30 vs. 39, p < 0.001). Similarly, patients with open fractures were more likely to be male (75 vs. 57%, p < 0.02), more likely to have been involved in a motorcycle crash (27 vs. 6%, p < 0.001), and more likely to have an unstable pelvic ring disruption (45 vs. 25%, p < 0.001). Open pelvic fracture patients required more blood than closed pelvic fracture patients, both in the first day (16 vs. 4 units, p < 0.001) and during the total hospital admission (29 vs. 9 units, p < 0.001). Five patients with perineal wounds did not receive a diverting colostomy; in turn, these individuals had a total of six pelvic infectious complications (one abscess, two with osteomyelitis, and three perineal wound infections). Overall, 11 patients died, six patients were lost to follow-up, and 27 were long-term survivors (mean duration of 4 years). Chronic disability was common after a pelvic fracture, with problems related to physical role performance and physical functioning, and was particularly severe after an open pelvic fracture (p < 0.05 for both as measured by the SF-36). CONCLUSIONS: Patients with open pelvic fractures often survive, need to be treated with massive blood transfusions, and often require a colostomy. They are frequently left with chronic pain and residual disabilities in physical functioning and physical roles, and many remain unemployed years after injury.     

Dynamic Properties of Highly Organic Soils from Montezuma Slough and Clifton Court

The nonlinear dynamic properties of highly organic soils from two levee sites in the Sacramento-San Joaquin Delta in California are described. Cyclic triaxial, resonant column and torsional shear tests were performed on thin-walled tube samples obtained from beneath levee crests, beneath adjacent berms, and in the free field such that the in situ vertical effective stresses (σvo′) ranged from about 16?to?67?kPa. These highly organic soils had considerably different organic characteristics from those used in previous studies of dynamic properties. The tested samples had organic contents of 14 to 61%, initial water contents (wo) of 88 to 496%, shear wave velocities (Vs) of 20?to?130?m/s, and organic components that ranged from highly fibrous to highly decomposed and amorphous. Secant shear modulus (G), normalized secant shear modulus (G/Gmax), and equivalent damping ratio (ξ) versus cyclic shear strain amplitude (γc) relations are presented, and their dependence on variables such as consolidation stress, organic content, prior loading history, testing device, and loading frequency are illustrated. Findings are compared to previously published results.