Mechanistic investigation and selectivity of the grafting onto C60 of macroradicals prepared by cobalt-mediated radical polymerization

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C₆₀ is investigated. The experimental conditions directly impact the nature and stability of the PVAc/C₆₀ adducts. In the presence of residual initiating radicals that can compete with PVAc° macroradicals for addition onto C₆₀, mixtures of PVAc/C₆₀ adducts having between one and eight polymer chains per C₆₀ are formed. PVAc/C₆₀ adducts prepared with low [PVAc]:[C₆₀] ratios may contain weak C₆₀–C₆₀ bonds that further dissociate and account for the instability of the products. The formation of such dimers can be lessened by increasing the temperature from 30 °C to 100 °C. The temperature increase also allows a complete dissociation of the PVAc-Co dormant species into PVAc° macroradicals and an almost quantitative grafting of eight PVAc chains onto C₆₀, leading to well-defined C₆₀(PVAc)₈ octa-adducts. These results might shed new light on the grafting onto C₆₀ of macroradicals prepared by other CRP techniques.     

Synthesis and characterizations of poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) copolymers

Poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) (EVOH-g-PHBV) was prepared by a catalyzed grafting of PHBV onto immiscible EVOH. These reactions were performed at high temperature in the molten state. The choices of Tin(II) bis(2-ethylhexanoate) (Sn(Oct)₂) and 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), as catalyst, were justified by a first study in an internal mixer. The catalyst quantity, reaction temperature and reaction time were optimized to apply them in the conditions of a reactive extrusion process with a co-rotating twin screw extruder. High reaction temperature, from 180 °C to 220 °C, associated to intensive mixing led to efficient grafting of PHBV onto EVOH, compatible with short residence times required.Rheological, thermal and morphological analyses were conducted to characterize the obtained copolymers. Molecular weights were determined by SEC. SEM imaging were made on cryo-fractured surfaces of blends extruded with and without catalyst. In most of reaction conditions, a compatible blend was obtained with a fine micro phase separation. Grafted copolymers were only obtained when well defined and controlled conditions are applied.     

Preliminary investigations of the production of MgAlON bonded refractories

The aim of the work was to find an appropriate composition for the formation of MgAlON bonding phase for Al₂O₃ and MgO based refractories. The first step was the preparation of pure MgAlON. AlN and Al₂O₃ were used as starting powders and either MgO or MgAl₂O₄ was added as a source of magnesium. The results verified the possibility to produce MgAlON under the prevailing conditions. Afterwards, MgAlON bonded alumina and magnesia refractories were investigated. The obtained results confirmed the possibility of the production of MgAlON bonded alumina refractories. However, in the case of magnesia-based samples MgAlON was not formed and instead stoichiometric spinel, AlN and alumina rich spinel were detected in the bonding phase. Additionally, the joining between the MgO grains and the matrix was poor with wide gaps on the interface.     

Extended studies of degradation mechanisms in the refractory lining of a rotary kiln for iron ore pellet production

Changes, over a period of 8 years, in the chemical composition and morphology of deposit and lining materials in a production rotary kiln for iron ore pellet manufacture are described. The following have been studied: two types of refractory brick used as lining material; deposited chunk materials from the lining; the interaction zones between deposits and linings. Morphological changes at the deposit/lining interface, and the active chemical reactions, are established. Larger hematite grains in the deposit material (5–50 μm) primarily remain at the original deposit/lining interface. The remainder penetrates fissures, voids and brick joints, forms a laminar structure with corundum from the bricks, and migrates in grains in the lining material. Potassium penetrates more deeply into the bricks than hematite, resulting in the formation of kalsilite, leucite and potassium β-alumina, which contribute to degradation of the lining.     

Bioactivity modulation of Bioglass® powder by thermal treatment

A discussion of the effects of Bioglass^® powder crystallisation on the in vitro bioactivity in simulated body fluid (SBF) is presented.Starting from Bioglass^® powder, different glass–ceramics were obtained by thermal treatments between 580 °C and 800 °C, with variable crystallisation content (from 10 to 92 wt%). All samples (glass and glass–ceramics) showed apatite formation at their surface when immersed in SBF. In case of the glass and the samples with lowest crystallinity, the first step of apatite formation involved a homogenous dissolution followed by an amorphous calcium phosphate (CaP) layer precipitation. For the samples with a high crystallisation content, heterogeneous dissolution occurred. For the first time, the Stevels number of the amorphous phase is used to explain the possible dissolution of the crystalline phase present in materials with a similar chemical composition of the Bioglass^®. All samples presented at 21 days of immersion in SBF B-type hydroxycarbonate apatite crystals.     

Identification of asymmetric constitutive laws at high temperature based on Digital Image Correlation

The mechanical characterization of ceramics can be very challenging. Depending on their composition and fabrication process, ceramic materials may exhibit at room temperature different types of mechanical behaviours, ranging from linear elastic to quasi-brittle, like rocks, concrete or plasters. At elevated temperature, they may present a non-linear behaviour, due for instance to the presence of a vitreous phase. However, estimating the evolution of their behaviour from room temperature to elevated temperature is a challenging topic, especially when there is an asymmetry between tension and compression. A methodology based on Digital Image Correlation is presented in this paper where four point bending tests are analysed for temperatures ranging from 25 °C to 900 °C. For a ceramic mainly made of aluminium titanate, the evolution of an asymmetric constitutive law is identified with a strong link with microstructural observations using SEM images.     

Dense bulk silicon oxycarbide glasses obtained by spark plasma sintering

Dense silicon oxycarbide glasses (SiOC) have been produced by spark plasma sintering (SPS) of SiOC powders. Raw powders were obtained by pyrolysis under nitrogen at 1100 °C of tetraethylorthosilcate/polydimethylsiloxane (TEOS/PDMS) hybrids. SPS experiments were carried out at 1300 and 1500 °C at 10 and 80 MPa and then were studied by chemical analysis, ²⁹Si and ¹³C MAS NMR, ATR, Raman, XRD, FE-SEM, density, porosity, microhardness (H_v) and thermal conductivity (K). The SiOC materials are formed by Si_xOC_4?x units within a silica matrix where silicon carbide and graphite nanodomains are also present. After the SPS treatment the silicon carbide crystallite size is close to 2.5 nm. At 1300 °C and 1500 °C the carbon nanodomain size is close to 3 nm and 2 nm, respectively. H_v values vary from 3.4 to 9.15 GPa, for 30% and 1% of porosity, respectively. Finally, K is always close to 1.38 W m^?1 K^?1.     

Electrical and mechanical characterization by instrumented indentation technique of La0.85Sr0.15Ga0.8Mg0.2O3−δ electrolyte for SOFCs

La_0.85Sr_0.15Ga_0.8Mg_0.2O_3?δ pellets obtained by the polymeric organic complex solution method, isostatic pressing and sintering at 1350 °C have been electrical and mechanically studied. Electrical measurements evidenced reasonable ionic conductivities (0.01 S cm^?1 at 800 °C), which were comparable to those reported for the La_1?xSr_xGa_1?yMg_yO_3?δ prepared by other synthesis methods. On the other hand, the mechanical properties (elastic modulus, E and hardness, H) have been determined at micro/nanometric scale using the instrumented indentation technique. While E did not vary significantly with the increasing indentation depth (h), H values strongly decreased with the indentation depth up to 500 nm. For h > 500 nm, both mechanical properties remained almost constant, thus obtaining E = 271 ± 6 GPa and H = 13.2 ± 0.4 GPa. Finally, the residual imprints and fracture mechanisms have been observed by atomic force microscopy (AFM).     

Improving Escherichia coli alkaline phosphatase efficacy by additional mutations inside and outside the catalytic pocket

We describe a strategy that allowed us to confer on a bacterial (E. coli) alkaline phosphatase (AP) the high catalytic activity of the mammalian enzyme while maintaining its high thermostability. First, we identified mutations, at positions other than those occupied by essential catalytic residues, which inactivate the bacterial enzyme without destroying its overall conformation. We transferred concomitantly into the bacterial enzyme four residues of the mammalian enzyme, two being in the catalytic pocket and two being outside. Second, the gene encoding the inactive mutant was submitted to random mutagenesis. Enzyme activity was restored upon the single mutation D330N, at a position that is 12 A away from the center of the catalytic pocket. Third, this mutation was combined with other mutations previously reported to increase AP activity slightly in the presence of magnesium. As a result, at pH 10.0 the phosphatase activity of both mutants D330N/D153H and D330N/D153G was 17-fold higher than that of the wild-type AP. Strikingly, although the two individual mutations D153H and D153G destabilize the enzyme, the double mutant D330N/D153G remained highly stable (T(m)=87 degrees C). Moreover, when combining the phosphatase and transferase activities, the catalytic activity of the mutant D330N/D153G increased 40-fold (k(cat)=3200 s-1) relative to that of the wild-type enzyme (k(cat)=80 s-1). Due to the simultaneous increase in K(m), the resulting k(cat)/K(m) value was only increased by a factor of two. Therefore, a single mutation occurring outside a catalytic pocket can dramatically control not only the activity of an enzyme, but also its thermostability. Preliminary crystallographic data of a covalent D330N/D153G enzyme-phosphate complex show that the phosphate group has significantly moved away from the catalytic pocket, relative to its position in the structure of another mutant previously reported.