Pyrolysis characteristics and kinetics of sewage sludge for different sizes and heating rates

The pyrolysis characteristics and kinetics of sewage sludge for different sizes (d < 0.25 mm, 0.25 mm < d < 0.83 mm, and d > 0.83 mm) and heating rates (5, 20, and 35 °C/min) were investigated in this article. The STA 409 was utilized for the sewage sludge thermogravimetric analysis. FTIR analysis was employed to study the functional groups and intermediates during the process of pyrolysis. Meanwhile, a new method was developed to calculate pyrolysis kinetic parameters (activated energy E, the frequency factor A, and reaction order n) with surface fitting tool in software MATLAB. The results show that all the TG curves are divided into three stages: evaporation temperature range (180–220 °C), main decomposition temperature range (220–650 °C), and final decomposition temperature range (650–780 °C). The sewage sludge of d < 0.25 mm obtains the largest total mass loss, especially at the heating rate of 5 °C/min. By FTIR analysis, the functional groups including NH, C–H, C=C, etc., are all found in the sewage sludge. There is a comparison between the FTIR spectra of sludge heated to 350 °C (temperature associated to maximum devolatilization rate in the second stage) and the FTIR spectra of sludge heated to 730 °C (temperature associated to maximum devolatilization rate in the third stage). In the second stage, the alcohols, ammonia, and carboxylic acid in the sludge have been mostly decomposed into gases, and only a little bit of compounds containing CH and OH of COOH exist. The pyrolysis kinetic parameters of second stage are as follows: the reaction orders are in the range of 1.6–1.8 and the activation energy is about 45 kJ/mol. The frequency factor increases with the increase of heating rate and sewage sludge size.     

On the temperature dependence of the order parameter of liquid crystals over a wide nematic range

Based on the ideas of Landau-de Gennes theory applied to nematic liquid crystals, several forms for the variation of the order parameter as a function of temperature are investigated over a wide nematic range. These functional forms are used to fit the experimental order parameters, determined through the use of C-13 NMR, for 4-methoxybenzylidene-4'-butylaniline (MBBA) and 4-n-pentyl-4'-cyanobiphenyl (5CB), and the physical significance of the parameters is discussed. A comparison of the results shows that the functional form which fits the experimental data best is similar to the Haller equation, a useful relation which is usually regarded as empirical. In this case, the coefficients resulting from a semi-empirical approach based on the Landau-de Gennes treatment may be thought of as quantifying the importance of the structure and rigidity of the liquid crystal in determining the temperature dependence of the order parameter for that liquid crystal. In the process, we have also examined the pretransitional behaviour in the C-13 NMR chemical shifts of liquid crystals observed within a few tenths of a degree above the nematic to isotropic transition temperature.     

On the temperature dependence of the order parameter of liquid crystals over a wide nematic range

Abstract

Based on the ideas of Landau-de Gennes theory applied to nematic liquid crystals, several forms for the variation of the order parameter as a function of temperature are investigated over a wide nematic range. These functional forms are used to fit the experimental order parameters, determined through the use of C-13 NMR, for 4-methoxybenzylidene-4′-butylaniline (MBBA) and 4-n-pentyl-4′-cyanobiphenyl (5CB), and the physical significance of the parameters is discussed. A comparison of the results shows that the functional form which fits the experimental data best is similar to the Haller equation, a useful relation which is usually regarded as empirical. In this case, the coefficients resulting from a semi-empirical approach based on the Landau-de Gennes treatment may be thought of as quantifying the importance of the structure and rigidity of the liquid crystal in determining the temperature dependence of the order parameter for that liquid crystal. In the process, we have also examined the pretransitional behaviour in the C-13 NMR chemical shifts of liquid crystals observed within a few tenths of a degree above the nematic to isotropic transition temperature.     

Polyethylene single crystals: Melting and morphology

Determination of important thermodynamic and physical properties of polymers has often been frustrated by the tendency of these materials to reorganize when heated. A novel technique has been developed which permits a more careful examination of the relationships existing between melting and morphology of single crystals. This has lead to the observation that high molecular weight polymers possess much narrower melting ranges than had been previously reported. By using this technique it has been possible to identify distinct transition temperatures for {100} and {110} fold sectors. DTA and DSC data have been previously reported for dried down single crystals. The applicability of this data to single crystals as they exist in suspension is questioned.     

Growth rates of protein crystals

Protein crystallization is important for structural biology. The rate at which a protein crystallizes is often the bottleneck in determining the protein's structure. Here, we give a physical model for the growth rates of protein crystals. Most materials crystallize faster under stronger growth conditions; however, protein crystallization slows down under the strongest conditions. Proteins require a crystallization slot of 'just right' conditions. Our model provides an explanation. Unlike simpler materials, proteins are orientationally asymmetrical. Under strong conditions, protein molecules attempt to crystallize too quickly, in wrong orientations, blocking surface sites for more productive crystal growth. The model explains the observation that increasing the net charge on a protein increases the crystal growth rate. The model predictions are in good agreement with experiments on the growth rates of tetragonal lysozyme crystals as a function of pH, salt concentration, temperature, and protein concentration.     

Cold drawing of it-polypropylene films of different thicknesses

Samples cut from it-polypropylene films of three different thicknesses are drawn at room temperature varying draw velocity. As characteristic variables of drawing process under neck formation yield stress, draw stress, neck propagation velocity and temperature of neck surface are measured. The characteristic variables are found to differ depending on thickness. The temperature rise of neck surface increases with growing thickness, whereas draw stress decreases. The variation of characteristic variables can partially be interpreted by thickness differences; for a complete understanding small morphological differences, depending on sample thickness, have to be taken into consideration.     

Melting behavior of poly-4-methyl-pentene-1 single crystals

Summary The present study described an investigation on differential scanning calorimetry (DSC) for isotactic poly-4-methyl-pentene-1 (P4MP1) single crystals. DSC was carried out in the following three procedures: (a) The crystals grown isothermally at various temperatures in n-hexadecane. tetralin, p-xylene. and decalin were heated at a constant heating rate of 80°C/min; (b) Some samples of crystals were heated at four kinds of heating rate, 80, 40, 10, and 5°C/min; (c) The crystals used in the above experiment (b) were irradiated to 14 Mrads with⁶⁰Co -ray. and these irradiated samples were heated at the same rate as in (b). Only the crystals from decalin revealed an endothermic peak in the vicinity of 80 °C (named as peak 1), which was concluded to originate from the solid-solid transition between two crystalline modifications. All crystals grown in various solvents gave a slightly observable endothermic peak in the vicinity of 125 °C (peak 2). The origin of peak 2, however, could not be determined whether it was based on a transition between crystalline modifications, or it merely reflected the abrupt change in the molecular motion at this temperature region. In high temperature region, two endothermic peaks that were inseparable from each other appeared (peak 3 and 4). The positions of peak 3 and 4, and the endothermic quantities of these peaks, from the above experiments (a). (b). and (c). were found to depend on crystallization condition and heating rate. These results could be explained well by considering that peak 3 corresponded to the melting of original single crystals, and peak 4 to the melting of the crystals with thicker lamellae that were formed in bulk during heating by partial melting and recrystallization. The introduction of the irradiation method helped us in investigating the origins of these four kinds of peak.

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Zusammenfassung Die vorliegende Studie beschreibt Untersuchungen mit Differentialthermoanalyse für isotaktische Poly-4-methyl-pentene-1 (P4MP1) Einkristallen. Die Differentialthermoanalyse wurde in folgender Weise ausgeführt. Erstens, die isotherm gewachsenen Kristalle der verschiedenen Temperaturen in n-Hexadecan, Tetralin, p-Xylol und Decalin wurden erhitzt mit konstanter Heizrate von 80°/min. Zweitens einige Kristallproben wurden bei 4 verschiedenen Heizgeschwindigkeiten 80. 40. 10 und 5°/min untersucht. Drittens die Kristalle in dem Experiment zwei wurden mit 14 Mrad einer Cobalt 60-Strahlungsquelle bestrahlt, und diese bestrahlten Proben wurden mit denselben Geschwindigkeiten wie in zwei erhitzt. Nur die Kristalle aus Decalin zeigten einen endothermen Peak in der Nachbarschaft von 80°, genannt Peak 1. Es wurde geschlossen, daß dieser Peak von einer Fest-Umwandlung zwischen zwei kristallinen Modifikationen herrührt. Alle Kristalle wurden gezüchtet aus den verschiedensten Lösungsmitteln und haben einen leicht beobachtbaren endothermen Peak in der Nachbarschaft von 125°. 2. Es konnte jedoch nicht festgestellt werden, ob dieser Peak 2 auch auf einer kristallinen Umwandlung zwischen Modifikationen beruht oder ob er nur eine plötzliehe Änderung in der molekularen Bewegung bei dieser Temperaturgegend andeutet. In höheren Temperaturbereichen treten zwei endotherme, nicht trennbare Peaks auf, Peak 3 und 4. Die Lagen von Peak 3 und 4 und die endtherme Größe dieser Peaks aus den Experimenten l, 2 und 3 waren abhängig von den Kristallisationsbedingungen und der Aufheizrate. Diese Ergebnisse lassen sich gut erklären durch die Betrachtung des Peak 3, der dem Schmelzen der Original-Einzelkristalle entspricht und Peak 4 dem Schmelzen der Kristalle mit dickeren Lamellen, die während des Aufheizens in der Masse durch partielles Schmelzen und Rekristallisation geformt wurden. Die Einführung der Bestrahlungsmethode half uns in der Peststellung des Ursprungs dieser 4 Arten von Peaks.

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The authors wish to express their appreciation to Dr.H.-D. Chu (Institute for Chemical Research, Kyoto University) and Mr.Y. Suzuki (Department of Polymer Chemistry. Kyoto University) for advice and help with⁶⁰Co -ray irradiation, and to Dr.T. Arakawa and Mr.N. Arai (Fiber and Textile Research Institute, Teijin Limited) for valuable discussion and help with differential scanning calorimetry.     

Anhydrous crystals of DNA bases are wide gap semiconductors

We present the structural, electronic, and optical properties of anhydrous crystals of DNA nucleobases (guanine, adenine, cytosine, and thymine) found after DFT (Density Functional Theory) calculations within the local density approximation, as well as experimental measurements of optical absorption for powders of these crystals. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.22 eV), respectively, while the experimentally estimated band gaps we have measured are 3.83 eV and 3.84 eV (3.89 eV and 4.07 eV), in the same order. The electronic effective masses we have obtained at band extremes show that, at low temperatures, these crystals behave like wide gap semiconductors for electrons moving along the nucleobases stacking direction, while the hole transport are somewhat limited. Lastly, the calculated electronic dielectric functions of DNA nucleobases crystals in the parallel and perpendicular directions to the stacking planes exhibit a high degree of anisotropy (except cytosine), in agreement with published experimental results.     

Non-isothermal degradation-based solid state kinetics study of copper (II) Schiff base complex,at different heating rates

The coordination complex of Cu (II) with the Schiff base derived from 4-chloroaniline with salicylaldehyde have been synthesized and characterized by micro analytical data; FT–IR, UV–Vis, FAB-mass and thermal analysis studies. Thermal data show degradation of complexes. We carried out thermal analysis at three different heating rates viz. 5, 10 and 20 °C per min. The activation thermodynamic parameters, such as activation energy (E*), entropy of activation (ΔS*), enthalpy of activation (ΔH*) and Gibbs free energy (ΔG*) have been calculated with the help of TG, DTA and DTG curves using Coats–Redfern method. The stoichiometry of the complexes are in 1:2 (M:L) molar ratio. Synthesized complex has been tested for their reactivity and substitution behaviour.     

Extended-chain crystals. IV. Melting under equilibrium conditions

Dilatometric melting experiments were performed on an extended-chain crystalline polyethylene with a broad molecular weight distribution and on four samples crystallized from fractionated polyethylenes. The melting curves were compared with computer calculations based on the assumption of eutectic separation. For the fraction of lowest molecular weight, agreement between experiment and calculation was achieved. The melting behavior of all other samples indicated that only for molecular weights up to 10,000–12,000 did eutectic separation occur. The higher molecular weight portion of each sample crystallized in the form of mixed crystals. Of the experimental maximum melting-point lowering of these mixed crystals, 0.1–0.9°C is due to the lower molecular weight diluents. Another 2–3°C lowering in melting point is due to the fact that the phase diagram of polyethylene mixed crystals has a minimum.     

Effect of heating rates on TG-DTA results of aluminum nanopowders prepared by laser heating evaporation

Aluminum (Al) nanopowders with mean diameter of about 50 nm and passivated by alumina (Al₂O₃) coatings were prepared by an evaporation route: laser heating evaporation. Thermal properties of the nanopowders were investigated by simultaneous thermogravimetric-differential thermal analysis (TG-DTA) in dry oxygen environment, using a series of heating rates (5, 10, 20, 30, 50 and 90°C min⁻¹) from room temperature to 1200°C. With the heating rates rise, the onset and peak temperatures of the oxidation rise, and the conversion degree of Al to Al₂O₃ varies. However, the specific heat release keeps relatively invariant and has an average value of 18.1 kJ g⁻¹. So the specific heat release is the intrinsic characteristic of Al nanopowders, which can represent the ability of energy release.     

Longitudinal growth of polymer crystals from flowing solutions. VI. Melting behavior of continuous fibrillar polyethylene crystals

The melting behavior of continuous fibrillar crystals of high-molecular-weight polyethylene has been investigated. The macrofibers were grown from dilute solutions in xylene subjected to Couette flow in the temperature range between 103 and 118.5°C. The thermograms, as determined by differential scanning calorimetry, exhibit three melting endotherms with peak temperatures at 141, 150.5, and 159.5°C after extrapolation to zero scan speed. All peaks were found to be strongly superheatable. Reduction of fiber length, in particular by etching with fuming nitric acid, led to the disappearance of the melting peaks at 150.5 and 159.5°C. The remaining peak at 136°C appeared not to be superheatable. The heat of fusion of the fragmented fibers was 69.8 cal/g. Wide-angle x-ray diffractograms taken on a macrofiber while gradually heated at a rate of 0.35°C/min at constant length showed that the triclinic phase present in the fiber disappeared at 130°C and that the orthorhombic cell transformed into the hexagonal modification at 150°C. This hexagonal phase was still observable at 180°C. The retractive force developed on heating at constant length displays first a slight decrease followed by a maximum at 150°C. Beyond the latter temperature the stress decays abruptly corresponding to the temperature at which fracture of the fiber could be observed visually. From all these observations it is inferred that the first melting endotherm in the differential scanning calorimeter (DSC) thermograms arises from the melting of unconstrained fibrillar crystal regions which are able to shrink during fusion. Moreover, the melting of lamellar overgrowths on the elementary fibrils on shish-kebab type may contribute to this endotherm. The second melting endotherm at about 150°C is associated with the transformation of the orthorhombic into the hexagonal lattice in constrained parts of the sample. This latter “rotator” phase allows slippage of the polymer chains past each other, giving rise to stress relaxation. The third endotherm arises from melting of this hexagonal phase and the heat take-up connected with the formation of higher energy gauche states upon randomization of the chains in the melt. Almost smooth, fully constrained fibrillar crystals grown at high temperature absorb more than 15.5 cal/g during this process, indicating that the polymer chains in such fibers must be highly extended.     

Melting temperature evolution of non-reorganized crystals. Poly(3-hydroxybutyrate)

In the present study the correlation between the melting behaviour of poly(3-hydroxybutyrate) (PHB) original, non-reorganized crystals and the crystallinity increase during isothermal crystallization is presented and discussed. Since the reorganization processes modify the melting curve of original crystals, it is necessary to prevent and hinder all the processes that influence and increase the lamellar thickness. PHB exhibits melting/recrystallization on heating, the occurring of lamellar thickening in the solid state being excluded. The first step of the study was the identification of the scanning rate which inhibits PHB recrystallization at sufficiently high T_c. For the extrapolated onset and peak temperatures of the main melting endotherm, which is connected to fusion of dominant lamellae, a double dependence on the crystallization time was found. The crystallization time at which T_onset and T_peak change their trends was found to correspond to the spherulite impingement time, so that the two different dependencies were put in relation with primary and secondary crystallizations respectively. The increase of both T_onset and T_peak at high crystallization times after spherulite impingement was considered an effect due to crystal superheating and an indication of a stabilization process of the crystalline phase. Such stabilization, which produces an increase of the melting temperature, is probably connected with the volume filling that occurs after spherulite impingement.     

Bacterial attachment over a wide range of ionic strengths

The number of bacterial cells adhered on a glass surface was counted over a wide range of ionic strengths. The counted number increased linearly with the square root of time. The rate of attachment increased with the increase in ionic strength and then plateaued. The rate of attachment was analyzed on the basis of the potential barrier between the surface of the bacterial cell and that of the substratum. An equation for formulating the dependence of the attachment rate on the ionic strength was proposed, which seems to be useful for the systematic understanding of bacterial attachment in various environments, from terrestrial to marine.     

Adsorption dynamics over a wide range of breakthrough concentrations

Conclusions A simple method is proposed for carrying out analytical calculations on adsorption dynamics; by its use one can make allowance for longitudinal effects in determining coefficients of external mass transfer and internal diffusion, and dynamic bed activities.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 56–62, January, 1981.     

Melting behavior of poly(butylene succinate) during heating scan by DSC

The melting behavior of isothermally crystallized poly(butylene succinate) (PBS) has been investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray analysis. The samples crystallized between 80°C to 100°C show middle endotherm at the position just before the high exotherm, while the others under 80°C show two endotherms (low and high). From the results of the melting peak vs. crystallization temperature plot, it was suggested that the middle endotherm corresponds to the melting process of the original crystallites and the high endotherms to the melting process of the recrystallized ones. As the DSC heating rate was increased, the peak temperature of the low and middle endotherms increased and that of the high endotherm decreased, indicating that the low endotherm was due to the original crystallites as well as the middle endotherm. Consequently, in the heating scan of PBS, the existence of two kinds of morphologically different crystallites as well as the process of melting and recrystallization becomes evident. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1357–1366, 1999     

Rotational dynamics and conformational kinetics in liquid crystals

Two particular aspects of solute dynamics in ordered media are analysed on the basis of the solution of multivariate diffusion equations: the effects of the solvation dynamics on the rotational motions of dipolar probes in liquid crystal solvents, and the alteration of reaction pathways in isomerization kinetics caused by the solvent order. The introduction of a suitable solvent coordinate allows the interpretation of high frequency contributions in the rotational correlation functions observed by spectroscopic techniques, namely dielectric dispersion, IR and Raman spectroscopy, ESR lineshapes and optical Kerr effect. For molecular systems undergoing conformational changes, a method is offered to evaluate the modification of the torsional barriers resulting from the anisotropic torques modulated by the molecular shape changes along the reaction coordinate.     

Rotational dynamics and conformational kinetics in liquid crystals

Abstract

Two particular aspects of solute dynamics in ordered media are analysed on the basis of the solution of multivariate diffusion equations: the effects of the solvation dynamics on the rotational motions of dipolar probes in liquid crystal solvents, and the alteration of reaction pathways in isomerization kinetics caused by the solvent order. The introduction of a suitable solvent coordinate allows the interpretation of high frequency contributions in the rotational correlation functions observed by spectroscopic techniques, namely dielectric dispersion, IR and Raman spectroscopy, ESR lineshapes and optical Kerr effect. For molecular systems undergoing conformational changes, a method is offered to evaluate the modification of the torsional barriers resulting from the anisotropic torques modulated by the molecular shape changes along the reaction coordinate.