Chemical Reaction Engineering and Research and development of gas solid systems

A general procedure is proposed for innovative research and development of gas-solid reactor systems, with a brief explanation of the significance of each step in the procedureBased upon the contacting mode between gas and solid phases, as well as the ways of supplying thermal energy to the reacting regions, various types of gas-solid reactor systems are classified by using tables of so called “matrix” form, for thermal cracking and gasification of heavy oils, gasification of coal, gasification of solid waste, calcination of limestone, clinkering of cement and reduction of iron ore.The importance of fundamental concepts is emphasized for successful research and development by presenting several examples; namely, calcination of limestone, thermal cracking of heavy oils and gasification of solid waste materials.In connection with the direction in which fundamental research should be oriented, four primary ways of thinking are proposed, which can be applied to obtain innovative ideas for further research and development in this field.One example of the author's practical experience was selected to show the role of the fundamental research in the course of large scale development. Finally the author outlines the role of chemical reaction engineering to innovate the novel gas-solid reactor systems which may be inevitable for simultaneous solution of the three big E's; namely, Energy, Environment and Economy.     

On the thermal stability of xanthan gum

The thermal stability of xanthan gum in dilute aqueous solutions at 90°C is considered. The relative viscosity as a function of ageing time is discussed, and it has been found to depend on the polymer concentration and conformation as well as on the salt content. The effectiveness of a quencher demonstrates the existence of a free-radical process in the degradation. During ageing, the molecular weight first decreases by rapid random hydrolysis of the main chain and loss of the pyruvate and acetate substituents. Later, oligomers are formed corresponding to a breakdown of both the side chain and the main chain. The identification of cellodextrins in the oligomer pool demonstrates the second effect.     

Thermal Expansion of Solid Solutions in the ZrTiO4—In2O3—M2O5 (M = Sb, Ta) System

Axial and dilatometric thermal expansions and phase transformations were studied for solid solutions having the α-PbO₂ structure in the ZrTiO₄—In₂O₃—M₂O₅ (M = Sb, Ta) system with nominal formulas of Zr _x Ti _y In _z Sb _z O₄ and Zr _x Ti _y In _z Ta _z O₄ where x + y + 2 z = 2. With increased substitution of z , the cell volume increased, the difference in the b parameters at room temperature between those quenched from 1400° and 1000°C decreased, and the thermal expansion decreased. The axial thermal expansion of ZrTi _y In _z · Ta _z O₄ with z = 0.3 was almost identical with that of HfTiO₄, and those with z = 0.4 and z = 0.45 were smaller than that of HfTiO₄. Unit-cell volumes of these compound were compared with those of single oxides to make it clear that the unit-cell volume of ZrTiO₄ was small anomalously and to distinguish the normal and abnormal substitution systems. These results were explained by the working hypothesis proposed for these compounds.     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

The Effect of Moisture Content in Epoxy Film Adhesives on their Performance. III: Bulk Properties

Humidity absorbed by epoxy film adhesives during low temperature storage or exposure to atmosphere may result in reversible changes and irreversible modifications. Vacuum treatment may partially remedy the reversible changes. The consequences of vacuum drying are manifested in enhancement of both the peel and shear properties of bonded joints (Part I and Part II of this series of papers) and the thermal, physical and mechanical properties of the bulk adhesive, characterized in the present study.

Experimental results have shown that the bulk properties of structural epoxy based adhesives are highly correlated with the aging processes caused by water absorption in the prepolymerized adhesive. Applying the vacuum process is harmful to fresh unaged adhesive due to devolatization of low molecular species of the film adhesive.

The characterization of bulk properties for the purpose of following the aging and recovery processes is advantageous, since the bulk is independent of geometrical and interfacial effects which dominate in the case of property evaluation of the adhesive in a bonded joint.     

Polysulphone and poly(phenylene sulphide) blends: 1. Thermal characterization and phase morphology

The phase behaviour and morphology of injection moulded specimens of polysulphone (PSF) and poly(phenylene sulphide) (PPS) blends were studied by differential scanning calorimetry (d.s.c.), dynamical mechanical thermal analysis (d.m.t.a.) and transmission electron microscopy (TEM). The blends are phase separated regardless of the blend composition as revealed by d.s.c., d.m.t.a. and TEM. Upon annealing at 160°C for 2 h, d.m.t.a. results indicate that the PPS phase remains in the amorphous state at compositions <10%. At compositions between 20 and 35%, the PPS appears to be dispersed in a mixed mode of amorphous and crystalline domains. Above 35% the PPS phase appears to become fully crystallized upon annealing of the blends. At 10% PPS, TEM results showed 35–200 nm size dispersion both in the as-moulded and in the annealed specimens. At 20% the PPS phase varied widely in size, from 35 nm to tens of micrometres but remained as an included phase. TEM also revealed a compound morphology of the included phase at a composition of 50 wt% of each component.     

Viscoelastic properties of cellulose derivatives: 1. Cellulose acetate

The dynamic mechanical spectrum of cellulose acetate (CA) from −130°C to 240°C has been determined at different frequencies (from 0.1 to 30 Hz). Three relaxations, designated , β and γ in order of decreasing temperature, and one shoulder (β*) above room temperature were found. Comparison with calorimetric and thermogravimetric measurements yields the conclusion that the relaxation (197°C at 3 Hz) is related to the glass-to-rubber transition and the β* shoulder (50°C–100°C) is due to loss of moisture. The β relaxation (−38°C at 3 Hz, ΔH = 100 kJ mol⁻¹) is tentatively assigned to local motions of the main chain (glucopyranose rings). The low-temperature γ relaxation (−88°C at 3 Hz, ΔH = 46 kJ mol⁻¹), is humidity-dependent: its intensity decreases when the samples are dried to moisture contents lower than that obtained by normal room conditioning (about 3%). Higher water contents shift the relaxation to lower temperatures without increasing the intensity of the mechanical loss. It is suggested that water associated with the unesterified methylol groups of cellulose acetate is responsible of the dynamic mechanical γ dispersion.     

Mullite for Structural, Electronic, and Optical Applications

Mullite (3Al₂O₃·2SiO₂) is becoming increasingly important in electronic, optical, and high-temperature structural applications. This paper reviews the current state of mullite-related research at a fundamental level, within the framework of phase equilibria, crystal structure, synthesis, processing, and properties. Phase equilibria are discussed in terms of the problems associated with the nucleation kinetics of mullite and the large variations observed in the solid-solution range. The incongruent melting behavior of mullite is now widely accepted. Large variations in the solid solubility from 58 to 76 mol% alumina are related to the ordering/disordering of oxygen vacancies and are strongly coupled with the method of synthesis used to form mullite. Similarly, reaction sequences which lead to the formation of mullite upon heating depend on the spatial scale at which the components are mixed. Mixing at the atomic level is useful for low-temperature (<1000°C) synthesis of mullite but not for low-temperature sintering. In contrast, precursors that are segregated are better suited for low-temperature (1250° to 1500°C) densification through viscous deformation. Flexural strength and creep resistance at elevated temperatures are significantly affected by the presence of glassy boundary inclusions; in the absence of glassy inclusions, polycrystalline mullite retains >90% of its room-temperature strength to 1500°C and displays very high creep resistance. Because of its low dielectric constant, mullite has now emerged as a substrate material in high-performance packaging applications. Interest in optical applications mainly centers on its applicability as a window material within the mid-infrared range.     

Transient Hot-Strip Method for Simultaneous Determination of Thermal Conductivity and Thermal Diffusivity of Refractory Materials

The transient hot-strip method has been used for determining thermal conductivity and thermal diffusivity of a refractory brick. The technique is based on recording the transient temperature increase of a 25-μm-thick, 8-mm-wide, and 70-mm-long iron strip clamped between two sample halves and heated with a constant direct current. The method is accurate to within 5% in the thermal conductivity and to within 10% in the thermal diffusivity in the temperature range 20° to 700°C.