Dependence of Silicon Carbide Product Morphology on the Degree of Mechanical Activation

Mechanical activation before carbothermic reduction can substantially enhance the formation of SiC from SiO₂and carbon mixtures. However, the morphology (e.g., particles or whiskers) of SiC formed from mechanically activated SiO₂and carbon mixtures is dependent of the degree of mechanical activation and the condition of the subsequent carbothermic reduction. These phenomena are investigated and rationalized based on the increased reactivity of the reactants and SiC formation mechanisms.     

Evolution and structure of drying material bridges of pharmaceutical excipients: studies on a microscope slide

An experimental procedure was developed to study directly the process by which liquid bridges between small particles in a granule form and solidify. The evolution of saturated solutions of such pharmaceutical excipients as lactose and mannitol in a liquid bridge was studied on a system situated on a microscope slide. Solidification and crystallization kinetics and phase composition during and immediately following bridge formation were observed directly. It was shown that bridges on the microscope slide and in the granule behave very much the same regardless of the different length and diffusion-scales of the two systems.We found that solid bridge formation takes place in several consecutive but distinct steps. In the case of lactose, considerable shrinkage of the initial liquid bridge takes place prior to the onset of crystallization. Further bridge solidification at ambient conditions occurs via simultaneous crystallization and vitrification within minutes. As a result, a “solid” bridge usually contains both a crystalline and a non-crystalline phase, the crystalline phase being predominately α-lactose monohydrate. Most of the non-crystalline phase eventually converts to crystalline β-lactose but the process may take many hours or even days. Results for this process are compared for samples obtained from different manufacturers of commercially available lactose. In the case of mannitol, different polymorphic forms crystallize as the drying/crystallization process progresses. A formed “solid” bridge usually contains several polymorphs of mannitol. The relevance of the behavior of the two model systems (pure lactose and pure mannitol) to a real granulation and tabletting process is discussed.     

Solvents effect on the physical properties of semi-dilute poly(N-isopropyl acryl amide) solutions

The physical properties of 5 wt% poly(NIPAM) (M_v=3.22×10⁵) semi-dilute solutions in H₂O, D₂O, and THF (tetrahydrofuran) solvents were studied using dynamic light scattering (DLS) and dynamic shear viscosity (DSV) measurements. The DLS data showed that there were poly(NIPAM) slow mode inter-polymer chains associations in H₂O and D₂O solvents. However, no DLS slow mode was observed in poly(NIPAM)/THF solutions. The DSV data showed that there are shear thickening behavior in these three poly(NIPAM) solutions, resulting in a maximum shear viscosity η_peak in the viscosity η′(ω) versus shear frequency ω curve. The slow mode hydrodynamic radius 〈R_hs〉 of DLS measurements and the zero shear rate viscosity η₀ and maximum viscosity η_peak data of DSV measurements from poly(NIPAM)/H₂O and poly(NIPAM)/D₂O solutions show two critical transition temperatures with T_cr1=30-32 °C and T_cr2=32-34 °C. Poly(NIPASM)/D₂O has higher T_cr1 and T_cr2 than poly(NIPASM)/H₂O. However, no transition temperatures of poly(NIPAM)/THF solution were observed. The different temperature dependencies of these three solutions were attributed to the ‘solubility’ and ‘hydrogen bonding’ effects between poly(NIPAM) with H₂O, D₂O, and THF solvents. Without considering the polymer-solvent hydrogen bonding, the solubility of poly(NIPAM) in solvents decreases in the following sequence: THF>H₂O>D₂O and the degree of polymer-solvent hydrogen bonding increases in the following sequence: THF<H₂O<D₂O. The effects of the degree of ‘hydrogen bonding’ and the ‘solubility’ of polymer in solvents on the physical properties of poly(NIPAM) solutions are discussed.     

Soft-and hard-segment phase segregation of polyester-based polyurethane

Polyester based polyurethanes were synthesized from 4,4′-methylene bis(phenyl isocyanate) (MDI) with butanediol as a chain extender and low molecular weight polyester-diol as a soft segment. Three polyesters were used in the synthesis of polyurethanes. Two of the polyesters, with molecular weight M_n = 2,660 and 2,155, were synthesized from adipic acid and 1,6-hexanediol, which had an even number of carbon atoms (polyester-6-6-1 and polyester-6-6-2). The other polyester with M_n = 2,770 was synthesized from pimelic acid and 1,5-pentanediol, which had an odd number of carbon atoms (polyester-7-5). Polyester-6-6-1 and polyester-6-6-2 consisting of even carbon monomers, had a higher degree of crystallinity at room temperature than polyester-7-5, which consists of an odd number of carbon monomers. The effect of polyester molecular weight and soft and hard-segmental geometric structure on the soft-and hard-segmental phase segregation was studied using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and small angle X-ray scattering (SAXS).     

Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

Yield stress distribution in injection‐moulded glassy polymers

A methodology for structural analysis simulations is presented that incorporates the distribution of mechanical properties along the geometrical dimensions of injection‐moulded amorphous polymer products. It is based on a previously developed modelling approach, where the thermomechanical history experienced during processing was used to determine the yield stress at the end of an injection‐moulding cycle. Comparison between experimental data and simulation results showed an excellent quantitative agreement, both for short‐term tensile tests as well as long‐term creep experiments over a range of strain rates, applied stresses, and testing temperatures. Changes in mould temperature and component wall thickness, which directly affect the cooling profiles and, hence, the mechanical properties, were well captured by the methodology presented. Furthermore, it turns out that the distribution of the yield stress along a tensile bar is one of the triggers for the onset of the (strong) localization generally observed in experiments. © 2015 Society of Chemical Industry     

Oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides

The oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides is reported. High yields of olefins and only moderate formation of carbon oxides was observed. Both are primary products that hardly interconvert under the reaction conditions used. Addition of chloride increases the rate of reaction, while slightly decreasing the selectivity to olefins. The addition of carbon dioxide strongly decreases the rate of reaction, the negative order of 0.5 indicating that two active Li⁺sites are blocked by the adsorption of one CO₂molecule. The reaction proceeds at low oxygen pressure primarily via elimination of dihydrogen, while at higher oxygen partial pressure the hydrogen elimination occurs via water formation. It is speculated that dehydrogenation and cracking involve Li⁺and a rather nucleophilic oxygen site.     

Phylogenetic Studies,Gene Cluster Analysis,and Enzymatic Reaction Support Anthrahydroquinone Reduction as the Physiological Function of Fungal 17β‐Hydroxysteroid Dehydrogenase

17β‐Hydroxysteroid dehydrogenase (17β‐HSDcl) from the filamentous fungus Curvularia lunata (teleomorph Cochliobolus lunatus) catalyzes NADP(H)‐dependent oxidoreductions of androgens and estrogens. Despite detailed biochemical and structural characterization of 17β‐HSDcl, its physiological function remains unknown. On the basis of amino acid sequence alignment, phylogenetic studies, and the recent identification of the physiological substrates of the homologous MdpC from Aspergillus nidulans and AflM from Aspergillus parasiticus, we propose an anthrahydroquinone as the physiological substrate of 17β‐HSDcl. This is also supported by our analysis of a secondary metabolite biosynthetic gene cluster in C. lunata m118, containing 17β‐HSDcl and ten other genes, including a polyketide synthase probably involved in emodin formation. Chemoenzymatic reduction of emodin by 17β‐HSDcl in the presence of sodium dithionite verified this hypothesis. On the basis of these results, the involvement of a 17β‐HSDcl in the biosynthesis of other anthrahydroquinone‐derived natural products is proposed; hence, 17β‐HSDcl should be more appropriately referred to as a polyhydroxyanthracene reductase (PHAR).     

Hybrid Neural Network Models Applied to a Free Radical Polymerization Process

This article presents different ways of obtaining hybrid models, which are composed of a simplified phenomenological model and one or several neural networks. As an example, we consider free radical polymerization of methyl methacrylate, achieved through a batch bulk process, in which modeling of conversion and polymerization degrees is analyzed. Kinetics of the process is described through a simplified phenomenological model that does not take into account the gel and glass effects. This last part of the process, which is more difficult to model, is rendered by means of feed-forward neural networks with one or two hidden layers. In the present paper, the hybridization procedure is made in three ways: 1) the neural network corrects the outputs of the simplified kinetic model by modeling the residuals of conversion and polymerization degrees; 2) the neural network provides accurate values of the rate constants to the simplified kinetic model; 3) the neural network models that part of the process in which gel and glass effects appear. It is demonstrated that accurate results are obtained in all three cases, and the hybrid models are easily created and manipulated, especially because they are based on neural networks with quite simple topologies.     

Incorporation of zinc into calcium silicate hydrates, Part I: formation of C-S-H(I) with C/S=2/3 and its isochemical counterpart gyrolite

We have investigated the incorporation of zinc into both nanocrystalline and crystalline calcium silicate hydrates with starting C/S ratios of 2/3 (0.66). Zinc was added replacing calcium in the starting mixtures [Zn/(Zn+Ca)=0-1/4; 0-10 wt.% Zn], and the resultant phases were characterised using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), differential thermal analysis-thermogravimetry (DTA-TG) and environmental scanning electron microscopy (ESEM).In both groups of samples, increasing zinc content led to gradual structural changes, until eventually a second phase was formed. Zinc was incorporated to similar limits in both sets of samples. The thermal stability of the structures increased to a certain zinc content, beyond which there was structural destabilisation. Zinc incorporation is possible up to ∼6 wt.%. Our observations strongly indicate similar zinc incorporation mechanisms in both sample series, namely incorporation of zinc into the interlayer of C-S-H(I) and the X-sheet of gyrolite for nanocrystalline and crystalline samples, respectively.