In-situ monitoring of changes in ultrastructure and mechanical properties of flax cell walls during controlled heat treatment.

Plant fibres are increasingly used as reinforcements, especially in thermoplastic composites. Understanding the impact of temperature on the properties of these fibres is an important issue for the manufacturing of high-performance materials with minimal defects. In this work, the structural evolution and mechanical behaviour of flax fibre cell walls were dynamically monitored by temperature-controlled X-ray diffraction and nanoindentation from 25 to 230 °C; detailed biochemical analysis was also conducted on fibre samples after each heating step. With increasing temperature up to 230 °C, a decrease in the local mechanical performance of the flax cell walls, of about -72 % for the indentation modulus and -35 % for the hardness, was measured. This was associated with a decrease in the packing of the cellulose crystal lattice (increase in d-spacing d200), as well as significant mass losses measured by thermogravimetric analysis and changes in the biochemical composition, i.e. non-cellulosic polysaccharides attributed to the middle lamellae but also to the cell walls. This work, which proposes for the first time an in-situ investigation of the dynamic temperature evolution of the flax cell wall properties, highlights the reversible behaviour of their crystalline structure (i.e. cellulose) and local mechanical properties after cooling to room temperature, even after exposure to high temperatures.

Incorporation of Fly Ash in Flame-Retardant Systems of Biopolyesters.

The incorporation of fly ash in polybutyl succinate (PBS) and polybutyl adipate terephtalate (PBAT) in the partial replacement of ammonium polyphosphate and/or melamine polyphosphate is evaluated in the present work. Furthermore, the influence of the surface modification of fly ash with two silanes and titanate coupling agents was also studied. Cone calorimeter experiments, pyrolysis combustion flow calorimeters (PCFCs), and UL94V tests were used to assess the fire performance of the composites. Scanning electronic microscopy, X-microanalysis, and X-ray diffractometry analysis were carried out on cone calorimeter residues in order to access the fire-retardant mode of action. The formation of new components due to the presence of fly ash was highlighted by X-ray diffractometry, indicating the synergistic effects between the flame-retardant system and fly ash. The X-microanalysis results showed that the main fraction of initial phosphorous is present in the cone calorimeter residue, indicating that the proposed system acts in a condensed phase.

Solid solutions between CrO4- and SO4-ettringite Ca6(Al(OH)6)2[(CrO4)x(SO4)(1-x)]3*26 H2O.

Chromate is a toxic contaminant of potential concern, as it is quite soluble in the alkaline pH range and could be released to the environment. In cementitous systems, CrO4(2−) is thought to be incorporated as a solid solution with SO4(2−) in ettringite. The formation of a solid solution (SS) could lower the soluble CrO4(2−) concentrations. Ettringite containing SO4(2−) or CrO4(2−) and mixtures thereof have been synthesized. The resulting solids and their solubility after an equilibration time of 3 months have been characterized. For CrO4-ettringite at 25 °C, a solubility product log K(S0) of −40.2 ± 0.4 was calculated: log K(CrO4−ettringite) = 6log{Ca2+} + 2log{Al(OH)4(−)} + 3log{CrO4(2−)} + 4log{OH−} + 26log{H2O}. X-ray diffraction and the analysis of the solution indicated the formation of a regular solid solution between SO4- and CrO4-ettringite with a miscibility gap between 0.4 ≤ XCrO4 ≤ 0.6. The miscibility gap of the SO4- and CrO4-ettringite solid solution could be reproduced with a dimensionless Guggenheim fitting parameter (a0) of 2.03. The presence of a solid solution between SO4- and CrO4-ettringite results in a stabilization of the solids compared to the pure ettringites and thus in an increased uptake of CrO4(2−) in cementitious systems.

Improved quantification of alite and belite in anhydrous Portland cements by (29)Si MAS NMR: effects of paramagnetic ions.

The applicability, reliability, and repeatability of 29Si MAS NMR for determination of the quantities of alite (Ca3SiO5) and belite (Ca2SiO4) in anhydrous Portland cement was investigated in detail for 11 commercial Portland cements and the results compared with phase quantifications based on powder X-ray diffraction combined with Rietveld analysis and with Taylor-Bogue calculations. The effects from paramagnetic ions (Fe3+) on the spinning sideband intensities, originating from dipolar couplings between 29Si and the spins of the paramagnetic electrons, were considered and analyzed in spectra recorded at four magnetic fields (4.7-14.1T) and this has led to an improved quantification of alite and belite from (29)Si MAS NMR spectra recorded at "high" spinning speeds of nu(R)=12.0-13.0kHz using 4 or 5mm rotors. Furthermore, the impact of Fe3+ ions on the spin-lattice relaxation was studied by inversion-recovery experiments and it was found that the relaxation is overwhelmingly dominated by the Fe3+ ions incorporated as guest-ions in alite and belite rather than the Fe3+ sites present in the intimately mixed ferrite phase (Ca2Al(x)Fe(2-)(x)O5).

Micropore size analysis in oil-well cement by proton nuclear relaxation.

The durability of cement depends mainly on cement microstructure parameters such as pore size distribution. In this study, we have observed pore size distribution in a Class G oil-well cement immersed for 1 year in brine at T = 293 K, P = 10(5) Pa and in a down-hole condition at T = 353 K, P = 7.10(6) Pa by proton nuclear magnetic spin-lattice relaxation (1H-NMR). After 4 months of immersion at T = 293 K, P = 10(5) Pa, the distribution of discrete relaxation rates reveals the fractal feature of the pore size distribution, whereas after 1 year at T = 353 K, P = 7.10(6) Pa, a dispersed distribution is still observed.

Through-bond phosphorus-phosphorus connectivities in crystalline and disordered phosphates by solid-state NMR.

2D 31P refocused INADEQUATE NMR experiments have been used to determine through-bond P-O-P connectivities in crystalline and disordered phosphates.