TiCl4(THF)2 impregnation on a flat SiOx/Si(1 0 0) and on polycrystalline Au foil: determination of surface species using XPS

TiCl₄(THF)₂ was impregnated by spin-coating on a Si(1 0 0) wafer covered with a thin SiO_x layer and on a polycrystalline Au foil. The nature of the surface species was determined at room temperature and after annealing, by X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM). A mixed Si:O:Ti interfacial layer was formed on the silicon substrate while in the case of Au, TiOCl_x and TiO_x were the main surface species at room temperature. Annealing at 723 K leads to the total desorption of the Cl atoms, and in both cases a significant amount of Ti atoms was reduced to the Ti³⁺ state. AFM measurements revealed a homogenous distribution of nano-sized TiO_x clusters with semi-ellipsoid shape and increased contact area with the underlying silica.     

Effects of CNT inclusions on structure and dielectric properties of PVDF/CNT nanocomposites

ABSTRACT

The effects of multiwall carbon nanotube (CNT) inclusions on the crystalline structure of poly(vinylidene fluoride) (PVDF), and on the dielectric properties of PVDF/CNT nanocomposites (NCs), prepared by melt mixing, were investigated by employing X-ray diffraction, differential scanning calorimetry, and dielectric spectroscopy techniques. Our results imply that, in the NCs, the formation of β-phase crystals depends on specific compression treatment in the melt and fast cooling. Dielectric measurements on NCs, with CNT concentrations below the electrical percolation threshold, reveal that the dielectric strength of the two relaxation processes in the amorphous phase and dielectric permittivity, ?′, measured within the broad temperature range from ?150 °C to 60 °C, increase strongly with increasing CNT concentration. This enhancement of amorphous PVDF polarizability has been attributed to the increase of the local electric field, due to local polarization generated at the surface of conductive inclusions/CNT clusters.     

Sandbed Consolidation with Mineral Precipitation

A new method has been developed to prevent sand reentrainment during oil production from unconsolidated or poorly consolidated reservoir formations. Consolidation of the zformation around the well is achieved through in situ precipitation of a sparingly soluble salt, namely, calcium phosphate. Control of the depth of salt formation is achieved by alternating injection, mixing, and reaction of two aqueous solutions of calcium chloride and potassium phosphate. Calcium phosphate crystals precipitate and grow on the grain surfaces, forming sufficiently uniform coatings. The formation of relatively uniform coatings on the grains causes an acceptably small decrease of the permeability, which is a feature of primary importance for oil production. The grains are gradually "cemented" with bridges of calcium phosphate crystallites and form a consolidated and still porous structure. As a result, the rate of hydrocarbon production for the problematic reservoir can be increased considerably without undesirable reentrainment of sand. The proposed method for consolidation has been successfully tested in sandbeds. Several series of experiments have been carried out under diverse conditions to establish the optimum parameter values for the implementation of this method. A set of optimum conditions at 25 degrees C were determined and these conditions gave satisfactory consolidation with permeability loss of ca. 60% of the initial value. The conditions of precipitation were chosen so that the precipitated phase was octacalcium phosphate [Ca(4)H(PO(4))(3).2.5H(2)O], along with its byproduct hydroxyapatite [Ca(5)(PO(4))(3)OH]. Experiments were also carried out at 70 degrees C and have shown that it is feasible to consolidate loose sandpacks at oil reservoir conditions. Copyright 2000 Academic Press.     

Precipitation of sparingly soluble salts in packed sandbeds in the presence of miscible and immiscible organic substances

Sparingly soluble salts precipitation, e.g. calcium carbonate or calcium sulfate, results in pore clogging in rock formations and in the concomitant reduction of the local permeability of oil wells during the oil extraction processes. On the other hand, in situ controlled salt precipitation is desirable in various applications e.g. waterproofing of concrete constructions suffering from leakages, etc. In the present study, calcium carbonate (CaCO₃) precipitation in sandbeds was investigated, in the presence of organic solvents simulating the conditions prevalent in oil‐well zones. CaCO₃ precipitation was investigated from supersaturated solutions prepared by in‐situ mixing of NaHCO₃ and CaCl₂.2H₂O solutions before the inlet of sandbeds. The solution resulting from the mixing of the two solutions was supersaturated with respect to all calcium carbonate polymorphs. Three types of experiments were performed depending on the supersaturated solutions: a) aqueous solutions b) aqueous supersaturated solutions in contact with sandbeds pre‐saturated with n‐dodecane c) aqueous solutions containing monoethylene glycol (MEG). Results showed that oil–water interfaces enhanced the heterogeneity of the supersaturated solutions and accelerated crystal growth of calcium carbonate at the inlet of the sandbed, resulting in early pore clogging and limitation of local permeability. Maximum sandbed consolidation was obtained with the solutions containing MEG.     

Ring‐Opening Metathesis Polymerization in Aqueous Media Using a Macroinitiator Approach

Water‐soluble and amphiphilic polymers are of great interest to industry and academia, as they can be used in applications such as biomaterials and drug delivery. Whilst ring‐opening metathesis polymerization (ROMP) is a fast and functional group tolerant methodology for the synthesis of a wide range of polymers, its full potential for the synthesis of water‐soluble polymers has yet to be realized. To address this, we report a general strategy for the synthesis of block copolymers in aqueous milieu using a commercially available ROMP catalyst and a macroinitiator approach. This allows for excellent control in the preparation of block copolymers in water. If the second monomer is chosen such that it forms a water‐insoluble polymer, polymerization‐induced self‐assembly (PISA) occurs and a variety of self‐assembled nano‐object morphologies can be accessed.     

Preparation of hybrid triple‐stimuli responsive nanogels based on poly(L‐histidine)

A series of novel multi‐responsive disulfide cross‐linked polypeptide nanogels has been synthesized by a one‐step ring‐opening polymerization process. The pH‐responsive core of the prepared nanogels was based on poly(L‐histidine), the difunctional N‐carboxy anhydride of l ‐cystine (l ‐Cys‐NCA) was used as a reduction‐cleavable cross‐linking agent, while the outer hydrophilic corona was comprised of a poly(ethylene oxide) block. Extensive molecular characterization studies were conducted in order to confirm the formation of the desired polymeric nanostructures and also to prove their responsiveness to external stimuli within the physiological values of healthy and cancer tissues. Furthermore, the disruption of the disulfide‐bond linkages between the polymeric chains was achieved by the presence of the reductive tripeptide glutathione (GSH), leading to size variations that were monitored by dynamic light scattering (DLS) and size‐exclusion chromatography (SEC). “Stealth” properties of the formed nanostructures were examined by zeta potential measurements. The described nanogels are clearly promising candidates for drug delivery applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1278–1288     

A Mathematical Radiobiological Model (MRM) to Predict Complex DNA Damage and Cell Survival for Ionizing Particle Radiations of Varying Quality

Predicting radiobiological effects is important in different areas of basic or clinical applications using ionizing radiation (IR); for example, towards optimizing radiation protection or radiation therapy protocols. In this case, we utilized as a basis the ‘MultiScale Approach (MSA)’ model and developed an integrated mathematical radiobiological model (MRM) with several modifications and improvements. Based on this new adaptation of the MSA model, we have predicted cell-specific levels of initial complex DNA damage and cell survival for irradiation with ¹¹Β, ¹²C, ¹⁴Ν, ¹⁶Ο, ²⁰Νe, ⁴⁰Αr, ²⁸Si and ⁵⁶Fe ions by using only three input parameters (particle’s LET and two cell-specific parameters: the cross sectional area of each cell nucleus and its genome size). The model-predicted survival curves are in good agreement with the experimental ones. The particle Relative Biological Effectiveness (RBE) and Oxygen Enhancement Ratio (OER) are also calculated in a very satisfactory way. The proposed integrated MRM model (within current limitations) can be a useful tool for the assessment of radiation biological damage for ions used in hadron-beam radiation therapy or radiation protection purposes.     

Polymerization-induced self-assembly and disassembly during the synthesis of thermoresponsive ABC triblock copolymer nano-objects in aqueous solution

Polymerization-induced self-assembly (PISA) has been widely utilized as a powerful methodology for the preparation of various self-assembled AB diblock copolymer nano-objects in aqueous media. Moreover, it is well-documented that chain extension of AB diblock copolymer vesicles using a range of hydrophobic monomers via seeded RAFT aqueous emulsion polymerization produces framboidal ABC triblock copolymer vesicles with adjustable surface roughness owing to microphase separation between the two enthalpically incompatible hydrophobic blocks located within their membranes. However, the utilization of hydrophilic monomers for the chain extension of linear diblock copolymer vesicles has yet to be thoroughly explored; this omission is addressed for aqueous PISA formulations in the present study. Herein poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (G-H) vesicles were used as seeds for the RAFT aqueous dispersion polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA). Interestingly, this led to polymerization-induced disassembly (PIDA), with the initial precursor vesicles being converted into lower-order worms or spheres depending on the target mean degree of polymerization (DP) for the corona-forming POEGMA block. Moreover, construction of a pseudo-phase diagram revealed an unexpected copolymer concentration dependence for this PIDA formulation. Previously, we reported that PHPMA-based diblock copolymer nano-objects only exhibit thermoresponsive behavior over a relatively narrow range of compositions and DPs (see Warren et al., Macromolecules, 2018, 51, 8357–8371). However, introduction of the POEGMA coronal block produced thermoresponsive ABC triblock nano-objects even when the precursor G-H diblock copolymer vesicles proved to be thermally unresponsive. Thus, this new approach is expected to enable the rational design of new nano-objects with tunable composition, copolymer architectures and stimulus-responsive behavior.

Chain extension of linear AB diblock copolymer vesicles by seeded RAFT aqueous dispersion polymerization using a hydrophilic monomer C leads to polymerization-induced disassembly to form lower-order thermoresponsive ABC triblock copolymer nano-objects.     

Ionic Nickel Embedded in Ceria with High Specific CO2 Methanation Activity

CO₂ hydrogenation to methane is gaining increasing interest as one of the most promising ways to store intermittent renewable energy in the form of chemical fuels. Ni particles supported on CeO₂ represent a highly efficient, stable and inexpensive catalyst for this reaction. Herein, Ni-doped CeO₂ nanoparticles were tested for CO₂ methanation showing an extremely high Ni mass-specific activity and CH₄ selectivity. Operando characterization reveals that this performance is tightly associated with ionic Νi and Ce³⁺ surface sites, while formation of metallic Ni does not seem to considerably promote the reaction. Theoretical calculations confirmed the stability of interstitial ionic Ni sites on ceria surfaces and highlighted the role of Ce-O frustrated Lewis pair (FLP), Ni-O classical Lewis pair (CLP) and Ni-Ce pair sites to the activation of H₂ and CO₂ molecules. To a large extent, the theoretical predictions were validated by in situ spectroscopy under H₂ and CO₂ : H₂ gaseous environments.