Characterisation of carbon blacks produced by solar thermal dissociation of methane

Solar methane dissociation appears as a possible route toward a hydrogen-based economy. The competitiveness of the process strongly depends on the carbon black properties and economic value. At CNRS-PROMES, a 50 kW tubular solar reactor was developed to produce carbon black and hydrogen from methane. The reaction was carried out in a graphite receiver crossed by seven graphite tubes heated up by concentrated solar radiations at the 1 MW CNRS solar furnace. The temperatures ranged between 1608 K and 1928 K and the methane flow-rates varied from 10.5 to 21 NL/min. Total methane dissociation was reached with hydrogen yield higher than 80% and the carbon yield was drastically affected by the acetylene by-product. The carbon samples were analysed in detail and their properties were compared to a commercial conductive grade carbon black. Transmission electron microscopy showed primary particles of 10–70 nm diameter. The crystallinity of the samples was characterised by Raman spectroscopy. It was also possible to correlate the specific surface area with the reaction temperature and with the concentrations of residual methane and of the acetylene by-product. The resistivity and the structure of the agglomerates were determined by simultaneous measurements of the conductivity and the density under compression.     

Dynamic methods and new reactors for liquid phase molecular catalysis

Kinetic data acquisition and screening of transition metal complexes for homogeneous liquid phase catalysis calls for numerous testing in multiphase G/L, L/L and G/L/L systems. It is shown first, with an example in asymmetric hydrogenation, why detailed kinetics must be performed. Then, new reactors leading to fast experimental techniques are proposed. A liquid–liquid centrifugal partition chromatography is evaluated for determining rate constants and partition isotherms by combining frontal analysis and elution chromatography, the catalyst being maintained in a stationary aqueous phase. Two microreactors offering short residence time have also been tested and compared with a fast test reaction (t_R ca. 5–20 s). The combination of reacting pulses, carrier liquids and micromixer is proposed as a general high throughput tool for the investigation of G/L, L/L and G/L/L catalytic systems in a fast sequential way.     

Development of blown film linear low-density polyethylene–clay nanocomposites: Part A: Manufacturing process and morphology

In this study, linear low-density polyethylene (LLDPE)/clay nanocomposites with different clay contents were prepared by melt intercalation using two different compatibilizers: maleic anhydride grafted styrene–ethylene–butylene–styrene and maleic anhydride grafted polyethylene (PE-g-MA). Melt intercalation was achieved by twin extrusion and nanocomposite films were produced by blown film extrusion. Effects of clay and compatibilizer fractions and type of compatibilizer on the structure, permeability, and the barrier properties of the nanocomposite films were investigated. PE-g-MA was shown to notably improve the dispersion of clay layers in the polyethylene matrix, and this was examined by atomic force microscopy and X-ray diffraction. The latter tests have also highlighted the importance of the screw configuration: the presence of mixing elements favors the dispersion and distribution of nanoclay. Moreover, differential scanning calorimetry results have shown no significant effect of the clay on the crystallinity of the composite while thermogravimetric analysis tests have demonstrated a decrease of onset and peak of decomposition temperatures. Finally, barrier properties toward water vapor transmission were measured. It was proven that not also clay, but the compatibilizer participated in decreasing the permeability of the film. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48589.     

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.     

A 3D EFFECT IN THE WEDGE ADHESION TEST: APPLICATION OF SPECKLE INTERFEROMETRY

The wedge test is of considerable use for evaluating adhesion between two bonded rigid substrates. In its (usual) static form, release of elastic strain energy is equated to effective adhesion energy during crack growth. However, the test is usually treated as two-dimensional. In fact, it is really three-dimensional due to anticlastic bending effects of the bent beam(s) during crack propagation.

We studied a composite material/epoxy/aluminium alloy system and observed a curved crack front during propagation. This leads to doubt as to the value of crack length to be inserted in the adhesion energy formula. In addition, by using the highly sensitive technique of speckle interferometry, it was possible to study anticlastic bending effects in a quantitative manner. Far from the crack front, agreement between theory and experimental is good, yet work remains to be done to understand the zone near the fracture zone.     

Synthesis of new polyester polyols from epoxidized vegetable oils and biobased acids

Biobased polyols were synthesized from reaction between epoxidized soybean oil and lactic, glycolic, or acetic acids. Polyols were characterized by NMR, alcohol and acid titration, and SEC. These analyses allowed to determine an average hydroxyl functionality between 4 and 5, with an oligomer content close to 50 wt%. Synthesized polyols were formulated with isocyanate to yield polyurethanes (PUs). Thermal and mechanical properties of obtained materials showed that synthesized polyols lead to rigid and brittle material with Young moduli higher than 900 N/mm² at RT and with T_g values around 50°C. Practical application: The products of the chemistry described in this contribution, i.e.: polyol from vegetable oils and lactic, glycolic, or acetic acids, provide biobased building blocks for further PUs syntheses by reaction with diisocyanates. The obtained PUs are partially biobased and may be applied as binders and coatings.     

Chemical Bond Between Stabilizers and HTPB Binders in Propellants

The character of the chemical bond between stabilizers and isocyanates used to cure the HTPB binder was determined. The aim was to explain, why it is not possible to extract some stabilizers from the binder of rocket motors. Investigations were performed by ¹H‐NMR‐spectroscopy on various combinations of stabilizers and isocyanates used to cure HTPB. It was demonstrated that stabilizes of some type can be attached to the polymeric network via a reaction with the di‐isocyanate. Criteria to evaluate the possibility of bonding the stabilizer to the network are derived. Finally the implication of the chemical bonding on the stabilizing effect is discussed.     

Deposition and characterisation of TiO2 coatings on various supports for structured (photo)catalytic reactors

Different types of aqueous TiO₂–P25 suspensions were prepared and their properties, including rheological behaviour and zeta potential, were studied. Then, TiO₂ suspensions were used to elaborate TiO₂ coatings on various substrates (cordierite monolith, stainless steel plates and -SiC foam) using a dip-coating method. The relationship between the suspension stability and the coating adhesion has been considered. The structural and morphological characterisation of TiO₂ coatings has been performed using scanning electron microscopy, X-ray diffraction and other methods. Finally, the photocatalytic properties of the materials have been determined by studying the photooxidation of aqueous ammonia.     

Structural and morphological control of aligned nitrogen-doped carbon nanotubes

Nitrogen-doped carbon nanotubes (CN_x-NTs) were prepared using a floating catalyst chemical vapor deposition method. Melamine precursor was employed to effectively control nitrogen content within the CN_x-NTs and modulate their structure. X-ray photoelectron spectroscopy (XPS) analysis of the nitrogen bonding demonstrates the nitrogen-incorporation profile according to the precursor amount, which indicates the correlation between the nitrogen concentration and morphology of nanotubes. With the increase of melamine amount, the growth rate of nanotubes increases significantly, and the inner structure of CN_x-NTs displayed a regular morphology transition from straight and smooth walls (0 at.% nitrogen) to cone-stacked shapes or bamboo-like structure (1.5%), then to corrugated structures (3.1% and above). Both XPS and CHN group results indicate that the nitrogen concentration of CN_x-NTs remained almost constant even after exposing them to air for 5 months, revealing superior nitrogen stability in CNTs. Raman analysis shows that the intensity ratio of D to G bands (I_D/I_G) of nanotubes increases with the melamine amount and position of G-band undergoes a down-shift due to increasing nitrogen doping. The aligned CN_x-NTs with modulated morphology, controlled nitrogen concentration and superior stability may find potential applications in developing various nanodevices such as fuel cells and nanoenergetic functional components.