Kinetics of reduction of iron oxides by H2: Part I: Low temperature reduction of hematite

This study deals with the reduction of Fe₂O₃ by H₂ in the temperature range of 220-680 °C. It aims to examine the rate controlling processes of Fe₂O₃ reduction by H₂ in the widest and lowest possible temperature range. This is to be related with efforts to decrease the emission of CO₂ in the atmosphere thus decreasing its green house effect.Reduction of hematite to magnetite with H₂ is characterized by an apparent activation energy ‘E_a’ of 76 kJ/mol. E_a of the reduction of magnetite to iron is 88 and 39 kJ/mol for temperatures lower and higher than 420 °C, respectively. Mathematical modeling of experimental data suggests that the reaction rate is controlled by two- and three-dimensional growth of nuclei and by phase boundary reaction at temperatures lower and higher than 420 °C, respectively.Morphological study confirms the formation of compact iron layer generated during the reduction of Fe₂O₃ by H₂ at temperatures higher than 420 °C. It also shows the absence of such layer in case of using CO. It seems that the annealing of magnetite's defects around 420 °C is responsible for the decrease of E_a.The rate of reduction of iron oxide with hydrogen is systematically higher than that obtained by CO.     

Synthesis, characterization and thermal degradation of 8-hydroxyquinoline-guanidine-formaldehyde terpolymer

Terpolymer (8-HQGF) has been synthesized using the monomers 8-hydroxyquinoline, guanidine, formaldehyde in 1:1:2 molar proportions. The structure of 8-HQGF terpolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e. UV-Visible, FTIR-ATR and ¹H NMR spectroscopy. Detailed thermal degradation study of the new terpolymer has been carried out to ascertain its thermal stability. Thermal degradation curve is discussed which shows two decomposition steps (265-475 °C and 540-715 °C). Sharp-Wentworth and Freeman-Carroll methods have been used to calculate activation energies and thermal stability. The activation energy (E_a) calculated by using the Sharp-Wentworth (21.98 kJ/mol) has been found to be in good agreement with that calculated by Freeman-Carroll (23.57 kJ/mol) method. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S^∗) and frequency factor (Z) have also been evaluated on the basis of the data of Freeman-Carroll method. The order of reaction (n) is found out to be 0.9979.     

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E_a = (54 ± 8) kJ/mol, and chloroform cast film, E_a = (69 ± 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of ∼10° at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the interbackbone planes reduces its intensity for higher temperatures. This last result could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments.     

Effects of temperature on the weathering of engineering thermoplastics

We have determined the activation energies (E_a) of yellowing and gloss loss for a large number of engineering thermoplastics and blends under accelerated weathering conditions. The E_a often depend on the property measured and exposure conditions, although they vary over a fairly small range. Under the CIRA/sodalime-filtered xenon arc conditions most likely to be representative of outdoor exposure, the E_a for gloss loss was ≤5 kcal/mol for all samples tested. The E_a for yellowing was also ≤5 kcal/mol except for SAN and ABS. Evidently the color bodies formed from photo-oxidation of SAN are more sensitive to temperature. A reaction with an E_a of 5 kcal/mol will increase its rate by about 33% for each 10 °C increase in temperature near room temperature. Temperature is an important, but not overwhelming, variable in the weathering of most engineering thermoplastics.     

Kinetics study on phase transformation from titania polymorph brookite to rutile

TiO₂ is a polymorphic material of great scientific interest due to its semiconductor properties and uses in heterogeneous photocatalysis. Understanding the stability of the polymorphs is important for designing TiO₂-based photocatalysts and solar cells. Although the phase transformation of anatase→rutile has been well studied, there is only one published work on brookite→rutile to date. The brookite→rutile transformation has been studied in this work using natural material from the Magnet Cove igneous complex mechanically processed to several micrometers in size. The pure phase brookite is annealed from 800 to 900 °C without detection of the anatase polymorph. The transformation kinetics are described by both the standard first-order model, with an activation energy of E_a=411.91 kJ/mol, and the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, with an activation energy of E_a=492.13 kJ/mol. The rate parameter of the first-order model for the phase transformation is expressed as k=6.85×10¹⁴ exp(−49,451/T) s⁻¹ for the first-order model and k=4.19×10¹⁸ exp(−59,189/T) s⁻¹ using the JMAK model. The obtained activation energy is higher than that of brookite nano-crystals. Our results show that the JMAK model fits the kinetics data better than other models.     

Nylon 6.6 accelerating aging studies: II. Long-term thermal-oxidative and hydrolysis results

Long-term (greater than 5 year exposures), low-temperature (as low as 37 °C) accelerated oven aging results were obtained for Nylon 6.6 fibers under thermo-oxidative conditions (air aging with an oxygen partial pressure of 13.2 cmHg in Albuquerque). To assess the importance of humidity on aging, experiments were also conducted under a combination of 100% RH plus 13.2 cmHg of oxygen partial pressure at temperatures ranging from 138 °C to 64 °C plus an additional experiment at 70% RH and 80 °C. The low-temperature tensile strength results showed that the Arrhenius activation energy under the pure oxidative degradation conditions dropped from ∼96 kJ/mol above ∼100 °C-∼30 kJ/mol below this temperature, indicative of a transition in the oxidative chemistry at low temperatures. Earlier work by our group on the same material concluded that hydrolytic degradation effects dominated oxidation effects at higher aging temperatures. However, the current long-term, low-temperature comparisons lead to the conclusion that humidity is not an important aging factor below ∼50 °C. By extrapolating time-temperature superposed oxidative degradation data using the low-temperature activation energy, we obtain predictions at 21 °C. At this temperature, we estimate that a tensile strength loss of 50% takes on the order of 70 years. The 21 °C predictions are shown to be reasonably consistent with long-term (up to 38 year) ambient results on similar Nylon materials removed from field-aged parachutes. Although the estimated average exposure temperature varies from parachute to parachute, the highest average temperature is estimated to be on the order of 21 °C.     

Lifetime predictions of EPR materials using the Wear-out approach

The Wear-out approach for lifetime prediction, based on cumulative damage concepts, is applied to several ethylene propylene rubber (EPR) cable insulation materials. EPR materials typically follow “induction-time” behavior in which their material properties change very slowly until just before failure, precluding the use of such time-dependent properties to predict failure. In the Wear-out approach, a material that has been aged at its ambient aging temperature T_a or at a low accelerated aging temperature is subsequently aged at a higher “Wear-out” temperature T_w in order to cause the material to reach its “failure” condition. In the simplest case, which involves the same chemical processes underlying degradation at T_a and T_w, a linear relationship is predicted between the time spent at T_a and the time required at T_w to complete the degradation. Data consistent with this expectation are presented for one of the EPR insulation materials. When the degradation chemistry at the two temperatures is different, a linear relationship between the time spent at T_a and the time required at T_w to complete the degradation is not generally expected. Even so, the Wear-out results for a second EPR material, which has evidence of changing chemistry, are reasonably linear and therefore useful from a predictive point-of-view. The Wear-out approach can therefore be used to transform non-predictive time-dependent material property results into predictive lifetime estimates. As a final example, the Wear-out approach is applied to an EPR insulation that had been aged in a nuclear power plant environment (∼51 °C) for times up to 23 years to show its likely viability for the hundreds of years predicted at this aging temperature from accelerated aging tests on EPR insulation materials.     

Nanocrystalline F-doped tin dioxide materials: texture, morphology and photosensitization with a perylene-substituted organotin

The controlled hydrolysis of fluoro(2-methylbutan-2-oxy)di(pentan-2,4-dionato)tin followed by annealing at 400-550 °C gave conductive mesoporous F-doped SnO₂ materials. The materials consist of a porous network of aggregated nanoparticles, the mesoporosity observed corresponding to the interparticle space. Tuning of the annealing temperature enabled us to prepare materials with surface areas ranging from 70 to 150 m² g⁻¹, with an average pore size comprised between 50 and 100 Å and with a mean particle diameter ranging from 50 to 120 Å. Resistivities as low as 1-2 Ω cm were measured for the sample treated at 550 °C which contained 2-3 at.% of fluorine. This powder reacted with 3-(6-trihex-1-ynylstannylhexyl)perylene to furnish a dye-sensitized F-doped SnO₂ mesoporous materials. An intensity-dependent photocurrent was produced under blue light illumination using the cavity microelectrode (CME) technique. With an aqueous NaBr solution, the photopotential reaches 700 mV, a value slightly higher than that found for an undoped sensitized SnO₂ powder (∼600 mV).     

Sample temperatures during outdoor and laboratory weathering exposures

Effective exposure temperatures (T_eff) in Arizona were calculated from hourly or 10-min parsed irradiation data along with ambient, black panel, and sample temperatures. The T_eff represents a constant temperature that creates the same amount of photodegradation as the naturally varying temperature and provides a benchmark temperature for making lifetime predictions from accelerated laboratory exposures. The annual ambient and black panel T_eff at a Wittmann, Arizona site were 30 °C and 42 °C, respectively, assuming that the photodegradation has an activation energy (E_a) of 21 kJ/mol (5 kcal/mol). T_eff was only weakly dependent on E_a over the range of 10-40 kJ/mol (3-10 kcal/mol). Samples exposed as van sunroofs were found to have T_eff that were offset from the black panel temperatures by a constant amount for the entire year. Thus, measurements of sample and black panel need to be made for only a few weeks to determine the offset and give the annual sample T_eff if the annual black panel T_eff is known. Light-colored samples probably are better compared with the ambient temperatures. Sample temperatures in xenon arc exposures usually are higher than the outdoor T_eff, so Arrhenius temperature corrections need to be carried out to relate accelerated to outdoor exposures. Temperatures in xenon arc exposure tests often correspond more closely to maximum temperatures that samples might encounter for only a few hours per year.     

Thermal degradation kinetics of the biodegradable aliphatic polyester, poly(propylene succinate)

The preparation of the biodegradable aliphatic polyester poly(propylene succinate) (PPSu) using 1,3-propanediol and succinic acid is presented. Its synthesis was performed by two-stage melt polycondensation in a glass batch reactor. The polyester was characterized by gel permeation chromatography, ¹H NMR spectroscopy and differential scanning calorimetry (DSC). It has a number average molecular weight 6880 g/mol, peak temperature of melting at 44 °C for heating rate 20 °C/min and glass transition temperature at −36 °C. After melt quenching it can be made completely amorphous due to its low crystallization rate. According to thermogravimetric measurements, PPSu shows a very high thermal stability as its major decomposition rate is at 404 °C (heating rate 10 °C/min). This is very high compared with aliphatic polyesters and can be compared to the decomposition temperature of aromatic polyesters. TG and Differential TG (DTG) thermograms revealed that PPSu degradation takes place in two stages, the first being at low temperatures that corresponds to a very small mass loss of about 7%, the second at elevated temperatures being the main degradation stage. Both stages are attributed to different decomposition mechanisms as is verified from activation energy determined with isoconversional methods of Ozawa, Flyn, Wall and Friedman. The first mechanism that takes place at low temperatures is auto-catalysis with activation energy E = 157 kJ/mol while the second mechanism is a first-order reaction with E = 221 kJ/mol, as calculated by the fitting of experimental measurements.     

A microwave and quantum chemical study of allyltrifluorosilane

The structural and conformational properties of allytrifluorsilane, H₂CCH-CH₂-SiF₃, have been explored by microwave (MW) spectroscopy and high-level ab initio and density functional theory quantum chemical calculations. The microwave spectrum was investigated in the 18-62 GHz spectral regions. The a-type R-branch transitions of one conformer were assigned for the ground as well as for 10 vibrationally excited states. The CC-C-Si chain of atoms in this rotamer takes an anti-clinal (‘skew’) conformation, with a dihedral angle calculated to be 111.6° from the syn-periplanar (0°) conformation. The question whether a CC-C-Si syn-periplanar conformer exists as a high-energy form in the gas phase remains open. In most of the quantum chemical calculations this conformation is predicted to be a transition state. However, in the most advanced calculations (B3LYP/aug-cc-pVTZ level of theory) the syn-periplanar conformer is predicted to be a stable rotamer that is calculated to be 6.5 kJ/mol higher in energy than the anti-clinal form. Since there is no indication in the MW spectrum for the presence of high-energy form(s), it is concluded that the anti-clinal conformer is at least 4 kJ/mol more stable than any other hypothetical rotamer.     

Quantitative studies on furfural and organic acid formation during hydrothermal,acidic and alkaline degradation ofD-xylose

Summary Chromatographic analysis of the degradation ofD-xylose either in plain water or aqueous sulfuric acid at temperatures ranging from 180 – 220°C gave up to 50 mol% of furfural. Activation energies did not differ significantly between reactions in plain water (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). However, under alkaline conditions the activation energy was only 63.7 kJ/mol, indicating a different reaction mechanism. Isotachophoretic analyses revealed the formation of pyruvic, formic, glycolic, lactic, and acetic acid. While the relative yields of these acids ranged from 0.8 to 7% under hydrothermal and acidic conditions, 10 – 23% were obtained in alkaline degradation.

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Quantitative Studien zur Bildung von Furfural und organischen Säuren während des hydrothermalen, sauren und alkalischen Abbaues vonD-Xylose

Zusammenfassung Die chromatographische Analyse des Abbaues vonD-Xylose in reinem Wasser und Schwefelsäure bei Temperaturen von 180 – 220°C ergab die Bildung von bis zu 50 mol% Furfural. In bezug auf die Aktivierungsenergie zeigten sich keine signifikanten Unterschiede zwischen dem Abbau vonD-Xylose in reinem Wasser (E _a =119.4 kJ/mol), 0.001M H₂SO₄ (E _a =120.6 kJ/mol), 0.01M H₂SO₄ (E _a =130.8 kJ/mol), and 0.1M H₂SO₄ (E _a =120.7 kJ/mol). Unter alkalischen Bedingungen hingegen betrug die Aktivierungsenergie nur 63.7 kJ/mol. Dies weist auf einen unterschiedlichen Reaktionsmechanismus hin. Ferner konnte mittels Isotachophorese die Bildung von Brenztraubensäure, Ameisensäure, Glycolsäure, Milchsäure und Essigsäure nachgewiesen werden. Während sich die relativen Ausbeuten in Wasser und Schwefelsäure zwischen 0.8 und 7% bewegten, betrugen sie unter alkalischen Bedingungen 10 bis 23%.

     

Kinetics of reduction of iron oxides by H2: Part II. Low temperature reduction of magnetite

This study deals with the reduction of Fe₃O₄ by H₂ in the temperature range of 210-950 °C. Two samples of Fe₃O₄ produced at 600 and 1200 °C, designated as Fe₃O₄₍₆₀₀₎ and Fe₃O_4(1200), have been used as starting material.Reduction of Fe₃O₄₍₆₀₀₎ by H₂ is characterized by an apparent activation energy ‘E_a’ of 200, 71 and 44 kJ/mol at T < 250 °C, 250 °C < T < 390 °C and T > 390 °C, respectively. The important change of E_a at 250 °C could be attributed to the removal of hydroxyl group and/or point defects of magnetite. This is confirmed during the reduction of Fe₃O_4(1200). While transition at T ≈ 390 °C is probably due to sintering of the reaction products as revealed by SEM.In situ X-rays diffraction reduction experiments confirm the formation of stoichiometric FeO between 390 and 570 °C. At higher temperatures, non-stoichiometric wüstite is the intermediate product of the reduction of Fe₃O₄ to Fe.The physical and chemical modifications of the reduction products at about 400 °C, had been confirmed by the reduction of Fe₃O₄₍₆₀₀₎ by CO and that of Fe₃O_4(1200) by H₂. A minimum reaction rate had been observed during the reduction of Fe₃O_4(1200) at about 760 °C. Mathematical modeling of experimental data suggests that the reaction rate is controlled by diffusion and SEM observations confirm the sintering of the reaction products.Finally, one may underline that the rate of reduction of Fe₃O₄ with H₂ is systematically higher than that obtained by CO in the explored temperature range.     

Thermal and mechanical properties of cationic guar gum/poly(acrylic acid) hydrogel membranes

Novel hydrogel membranes (coded as GA) based on cationic guar gum (CGG) and poly(acrylic acid) (PAA) were synthesized with various feed compositions. Their structure and properties were studied by Fourier transform infrared spectra, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analyses and tensile tests. The structure analyses indicated that there existed strong electrostatic interaction between CGG and PAA, which resulted in uniform structure and complete miscibility between the two components. On the basis of thermogravimetric analyses, the activation energies (E_a) of the first degradation of the membranes increased from 34.5 to 77.1 kJ/mol with an increase of CGG content, while the residual ratios of the membranes increased from 7.6 to 36.1 wt% at 600 °C. This indicated an elevated thermal stability of PAA-based materials through an introduction of CGG. The tensile tests exhibited the mechanical properties of the membranes were improved with an increase of CGG content, and the maximum value of 41.1 MPa was reached.     

Extremely facile ring inversion and rearrangement in fluorobicyclo[2.1.0]pentanes

cis-1,2,3,4,5,5-Hexafluorobicyclo[2.1.0]pentane and 1,2,4,5-tetrafluorobicyclo[2.1.0]pentane have been synthesized from hexafluorobenzene. The former hydrofluorocarbon, which exists entirely in the endo configuration, rearranges to cis-1,2,3,3,4,5-hexafluorocyclopentene below room temperature (E_a = 21.9 kcal/mol, log A = 13.4). The latter undergoes degenerate ring inversion with extraordinary ease (ΔG^‡ = 6.8 ± 0.2 kcal/mol at −55 °C). Density functional calculations indicate that significant bonding between the bridgehead carbons is retained in the ring inversion transition state. Analogous calculations predict for hexafluorobicyclo[1.1.0]butane a considerably lower barrier for ring inversion and more 1,3-bonding in the transition state.     

Effects of temperature on the weathering lifetime of coated polycarbonate

The lifetime of polycarbonate (PC) coated with silicone hardcoats containing UV absorber is shorter at elevated temperatures. The activation energy (E_a) for delamination was found to be 18 ± 2 kJ/mol (4.3 ± 0.5 kcal/mol) at the 95% confidence level in this study. This E_a is the consequence of the sensitivity of the substrate and the UV absorber to temperature. The E_a for PC photodegradation was previously found to be 17-21 kJ/mol (4-5 kcal/mol). The E_a for loss of absorbance in the second-generation silicone hardcoat was found to be 28.5 ± 5.4 kJ/mol (6.8 ± 1.3 kcal/mol) at the 95% confidence level. Results are consistent with experimental findings when these activation energies are used in published predictive models. Since the E_a for coating delamination depends on the E_a of UV absorber loss, coating systems different from the one in this study will need to be investigated separately.     

Condition monitoring methods applied to degradation of chlorosulfonated polyethylene cable jacketing materials

Three promising polymer material condition monitoring (CM) methods were applied to eight commercial chlorosulfonated polyethylene cable jacket materials aged under both elevated temperature and high-energy radiation conditions. The CM methods examined, cross-sectional modulus profiling, solvent uptake and NMR T₂ relaxation time measurements of solvent-swelled samples, are closely related since they are all strongly influenced by the changes in overall crosslink density of the materials. Each approach was found to correlate well with ultimate tensile elongation measurements, the most widely used method for following degradation of elastomeric materials. In addition approximately universal failure criteria were found to be applicable for the modulus profiling and solvent uptake measurements, independent of the CSPE material examined and its degradation environment. For an arbitrarily assumed elongation “failure” criterion of 50% absolute, the CSPE materials typically reached “failure” when the modulus increased to ∼35 MPa and the uptake factor in p-xylene decreased to ∼1.6.     

Investigation of thermal degradation mechanism of an aliphatic polyester using pyrolysis-gas chromatography-mass spectrometry and a kinetic study of the effect of the amount of polymerisation catalyst

The thermal degradation mechanism of the aliphatic biodegradable polyester poly(propylene succinate) (PPSu) and the effect of the polymerisation catalyst (tetrabutyl titanate, TBT) were studied using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and TGA analysis. It is found from mass ions detection, that the decomposition takes place, mainly, through β-hydrogen bond scission and secondarily by α-hydrogen bond scission. At low pyrolysis temperatures (360 and 385 °C) gases as well as succinic anhydride, succinic acid and propanoic acid are mainly produced while allyl and diallyl succinates are formed in smaller quantities. At high temperatures (450 °C) the behaviour is inverted. Using the isoconversional methods of Ozawa and Friedman it is founded that PPSu degrades by two consecutive mechanisms. According to this analysis the first mechanism that takes place at low temperatures is autocatalysis with an activation energy of about E = 110-120 kJ/mol. The second mechanism is a first-order reaction with E of 220 kJ/mol, and corresponds to the extended β- and α-hydrogen bond scissions. These activation energies are slightly dependent on the catalyst amount and are shifted towards lower values with an increase of TBT content from 3 × 10⁻⁴ to 3 × 10⁻¹ mol TBT/mol succinic acid (SA).     

Thermal degradation mechanism of poly(ethylene succinate) and poly(butylene succinate): Comparative study

Two aliphatic polyesters that consisted from succinic acid, ethylene glycol and butylene glycol, —poly(ethylene succinate) (PESu) and poly(butylene succinate) (PBSu)—, were prepared by melt polycondensation process in a glass batch reactor. These polyesters were characterized by DSC, ¹H NMR and molecular weight distribution. Their number average molecular weight is almost identical in both polyesters, close to 7000 g/mol, as well as their carboxyl end groups (80 eq/10⁶ g). From TG and Differential TG (DTG) thermograms it was found that the decomposition step appears at a temperature 399 °C for PBSu and 413 °C for PESu. This is an indication that PESu is more stable than PBSu and that chemical structure plays an important role in the thermal decomposition process. In both polyesters degradation takes place in two stages, the first that corresponds to a very small mass loss, and the second at elevated temperatures being the main degradation stage. The two stages are attributed to different decomposition mechanisms as is verified from the values of activation energy determined with iso-conversional methods of Ozawa, Flyn, Wall and Friedman. The first mechanism that takes place at low temperatures, is auto-catalysis with activation energy E = 128 and E = 182 kJ/mol and reaction order n = 0.75 and 1.84 for PBSu and PESu, respectively. The second mechanism is nth-order reaction with E = 189 and 256 kJ/mol and reaction order n = 0.68 and 0.96 for PBSu and PESu, respectively, as they were calculated from the fitting of experimental results.