Minor Decomposition Research Articles

Separation of siderite from calcite by differential reaction with dilute ethanoic acid: mineralogical and isotopic (δ13C, δ18O) effects

ABSTRACT A simple procedure is described for the separation of siderite, from mixtures of siderite and calcite, for carbon and oxygen isotope analysis based on the selective decomposition of calcite by reaction with stoichiometric excess ethanoic acid. Artificial mixtures, prepared from two naturally occurring materials (concretionary siderite containing approximately equal quantities of low-Mg and high-Mg siderite, and low-Mg calcite), are used to test the selectivity of calcite removal, investigate the potential for differential acid decomposition of siderites of differing geochemical composition, and assess the effect of separation procedures on the isotopic composition of recovered carbonate. Acidification results in complete removal of calcite and only minor (< 2 wt %) siderite decomposition. Isotopic effects are limited with minimal difference between untreated (experimental control) and acid-treated materials. Discrepancies are attributed to preferential decomposition (greater reactivity) of (low δ13C, δ18O) high-Mg over (high δ13C, δ18O) low-Mg siderite in moderately acidic solvents. Observed departures from true isotopic compositions are insignificant for most geochemical applications when compared with other sources of uncertainty associated with the interpretation of siderite stable-isotope data sets in natural systems.

Research on dolomite-based shape-stabilized phase change materials for thermal energy storage: Feasibility study of raw and calcined dolomite as skeleton support materials

Mid and high-temperature inorganic salts have limited applications due to their corrosiveness and low thermal conductivity. Shape-stabilized phase change materials (SSPCMs) can ease these issues. This study explored using dolomite, an affordable and abundant mineral with good thermal properties, in SSPCMs. We developed SSPCMs using raw and calcined dolomite at 700 °C, 750 °C, and 800 °C (700Do, 750Do and 800Do) as skeletal support materials (SSMs) and NaNO3-KNO3 as the phase change materials (PCMs). Calcined dolomites had a porous structure compared to raw dolomite (RawDo). 700Do, 750Do and 800Do require a minimum of 50 wt%, 40 wt% and 30 wt% to stabilize the shape of the sintered material by 100 cycles. RawDo was unsuitable for SSM during cycling. XRD confirmed chemical compatibility between components, and SEM showed an even distribution of SSMs within the PCMs. The thermal conductivity of SSPCMs ranged from 1.09 to 1.27 W/(m·K), compared to 0.52 W/(m·K) for NaNO3-KNO3. The NaNO3-KNO3 has a latent heat of about 110.60 J/g and a supercooling degree of 5.84 °C. The latent heat of SSPCMs depends on the proportion of SSMs, slightly lower than the theoretical value by 0.01 %–2.37 %, and the supercooling degree of SSPCMs varies between 4.75 °C and 6.25 °C. The SSPCMs were chemically stable with little latent heat change after 100 cycles, showing excellent cycling stability. The thermal decomposition temperature of SSPCMs containing 700Do was about 580 °C, while SSPCMs containing 750Do and 800Do exhibited a minor decomposition onset at around 380 °C, attributed to Ca(OH)2 decomposition. The best-performing SSPCM contained 30 wt% 800Do, offering a thermal conductivity of 1.27 W/(m·K) and thermal energy storage density of 359 kJ/kg in the 100–320 °C range. In general, calcined dolomite-based SSPCMs offer excellent thermal energy storage performance at a low cost compared to many SSPCMs.

Developing terpyridine-based metal complexes for non-aqueous redox flow batteries

This paper describes the design and synthesis of a series of terpyridine-based complexes of the first-row transition metals Cr, Mn, Fe, and Co for non-aqueous redox flow batteries (NARFBs). Electrochemical studies reveal that these complexes can undergo multi-electron transfer redox reactions. In particular, the Mn and Fe-based complexes exhibit both low negative redox potentials and high positive redox potential, permitting them to serve as a bipolar electrolyte for symmetric RFBs with a cell voltage of more than 2 V. The solubility of these complexes can be effectively improved by incorporating a polyether substituent on the terpyridine ligand and counter anion optimization. The iron complex [Fe(tpy-O(CH2CH2O)3CH3)2][TFSI]2 shows a high solubility of 0.76 M in MeCN. The fabricated iron-based symmetric NARFB demonstrates a superior battery performance with a high cell voltage of 2.3 V, columbic efficiency of 97%, energy efficiency as high as 88%, and stable charge-discharge capacity retention of 60% after 160 cycles, corresponding to 99.75 % capacity retention per cycle. The post-cycling cyclic voltammetry (CV), UV-Vis, and 1H-NMR characterizations indicate only minor chemical decomposition of the cycled complex, confirming its good charging-discharging stability.

Thermal Behavior of Poly(vinyl alcohol) in the Form of Physically Crosslinked Film.

Evaluation and understanding of the thermal behavior of polymers is crucial for many applications, e.g., polymer processing at relatively high temperatures, and for evaluating polymer-polymer miscibility. In this study, the differences in the thermal behavior of poly(vinyl alcohol) (PVA) raw powder and physically crosslinked films were investigated using various methods, such as thermogravimetric analysis (TGA) and derivative TGA (DTGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Various strategies were adopted, e.g., film casting from PVA solutions in H2O and D2O and heating of samples at carefully selected temperatures, in order to provide insights about the structure-properties relationship. It was found that the physically crosslinked PVA film presents an increased number of hydrogen bonds and increased thermal stability/slower decomposition rate compared to the PVA raw powder. This is also depicted in the estimated values of specific heat of thermochemical transition. The first thermochemical transition (glass transition) of PVA film, as for the raw powder, overlaps with mass loss from multiple origins. Evidence for minor decomposition that occurs along with impurities removal is presented. The overlapping of various effects (softening, decomposition, and evaporation of impurities) has led to confusion and apparent consistencies, e.g., from the XRD, it is derived that the film has decreased crystallinity, and apparently this is in agreement with the lower value of heat of fusion. However, the heat of fusion in this particular case has a questionable meaning.

Radiation Resistance and Adsorption Behavior of Aluminum Hexacyanoferrate for Pd.

Irradiation resistance is important for adsorbents used in radioactive environments such as high-level liquid waste. In this work, a silica-based composite adsorbent (KAlFe(CN)6/SiO2) was synthesized and γ-irradiated from 10 to 1000 kGy. The angles of the main X-ray diffraction peaks slightly decreased with the increase in irradiation dose, and a minor decomposition of CN- occurred after irradiation to 1000 kGy, indicating that the KAlFe(CN)6/SiO2 adsorbent could preserve structural integrity with a dose below 100 kGy. In 1 to 7 M HNO3, the adsorption ability of the irradiated KAlFe(CN)6/SiO2 remained performant, with a higher Kd than 1625 cm3 g-1. The adsorption equilibrium of Pd(II) in 3 M HNO3 was attained within 45 min before and after irradiation. The maximal adsorption capacity Qe of the irradiated KAlFe(CN)6/SiO2 on Pd(II) ranged from 45.1 to 48.1 mg g-1. A 1.2% relative drop in Qe was observed after 100 kGy irradiation, showing that γ-irradiation lower than 100 kGy insignificantly affected the adsorption capacity of KAlFe(CN)6/SiO2. Calculating and comparing the structures and free energies of different adsorption products via the density functional theory (DFT) method showed that KAlFe(CN)6/SiO2 was more inclined to completely adsorb Pd(II) and spontaneously generate Pd[AlFe(CN)6]2.

Catalytical thermal conversion of waste fishing nets for a higher added value energy products generation and caprolactam recovery

The ongoing eutrophication processes and water pollution caused by marine plastic waste are relevant ecological problem. Collected wastes are possible alternative feedstock for additional higher added value energy product generation. Moreover, caprolactamis the main compound of nylon-6 waste fishing nets and its recovery conserves natural resources, maximizes waste economic performance, and closes the circular economy loop of the fishing net industry. In order to contribute to the creation of circular economy, investigation of pyrolysis process and the effect of catalyst synergy with different temperatures on the formulated products has been performed. This work aims to analyse the used fishing nets (FN), using TGA-DTG-FTIR systems and mini pyrolysis plant. Experiments were conducted with Y-type zeolite and ZSM-5 as catalysts with a ratio of 1 by 3 and 1 by 8, respectively. Micro-thermal analysis using the TGA-DTG-FTIR system was processed for feedstock characterization purposes, which showed that the fishing gear has one minor decomposition peak around 200 °C, and the major one around 450 °C, with a total weight loss of 88 wt%. Pyro-oils analysis showed that the main fractions could be assigned to aromatic and aliphatic hydrocarbons, such as naphthalene, styrene, and toluene. Moreover, the recovery of caprolactam shows a possibility to obtain not only energy products, but also higher added value chemical derivatives. Temperature and catalyst synergetic approach influence for the recovered products investigation showed the optimum conditions as 700 °C for the highest purity and quality products generation. Based on the results, catalytic thermal treatment at 700 °C with Y-Type could be adapted as a promising technique for extracting of caprolactam with a high yield (96 %).

Genetic Relationship between Mississippi Valley-Type Pb–Zn Mineralization and Hydrocarbon Accumulation in the Wusihe Deposits, Southwestern Margin of the Sichuan Basin, China

The coexistence of numerous Mississippi Valley-type (MVT) Pb–Zn deposits and oil/gas reservoirs in the world suggests a close genetic relationship between mineralization and hydrocarbon accumulation. The Wusihe MVT Pb–Zn deposits are located along the southwestern margin of the Sichuan Basin. Based on the spatiotemporal relation between Pb–Zn deposits and paleo-oil/gas reservoirs, ore material sources, and processes of mineralization and hydrocarbon accumulation, a new genetic relationship between mineralization and hydrocarbon accumulation is suggested for these deposits. The Wusihe Pb–Zn deposits are hosted in the Ediacaran Dengying Formation dolostone, accompanied by a large amount of thermally cracked bitumen in the ore bodies. The Pb–Zn deposits and paleo-oil/gas reservoirs are distributed along the paleokarst interface; they overlap spatially, and the ore body occupies the upper part of the paleo-oil/gas reservoirs. Both the Pb–Zn ore and sphalerite are rich in thermally cracked bitumen, in which µm sized galena and sphalerite may be observed, and the contents of lead and zinc in the bitumen are higher than those required for Pb–Zn mineralization. The paleo-oil/gas reservoirs experienced paleo-oil reservoir formation, paleo-gas reservoir generation, and paleo-gas reservoir destruction. The generation time of the paleo-gas reservoirs is similar to the metallogenic time. The source rocks from the Cambrian Qiongzhusi Formation not only provided oil sources for paleo-oil reservoirs but also provided ore-forming metal elements for mineralization. Liquid oil with abundant ore-forming metals accumulated to form paleo-oil reservoirs with mature organic matter in source rocks. As paleo-oil reservoirs were buried, the oil underwent in situ thermal cracking to form overpressure paleo-gas reservoirs and a large amount of bitumen. Along with the thermal cracking of the oil, the metal elements decoupled from organic matter and H2S formed by thermochemical sulfate reduction (TSR) and minor decomposition of the organic matter dissolved in oilfield brine to form the ore fluid. The large-scale Pb–Zn mineralization is mainly related to the destruction of the overpressured paleo-gas reservoir; the sudden pressure relief caused the ore fluid around the gas–water interface to migrate upward into the paleo-gas reservoirs and induced extensive metal sulfide precipitation in the ore fluid, resulting in special spatiotemporal associated or paragenetic relations of galena, sphalerite, and bitumen.

Vapor phase polymerization of Ag QD-embedded PEDOT film with enhanced thermoelectric and antibacterial properties

Nonferric oxidant precursors have the unique advantage of directly polymerizing poly(3,4-ethylenedioxythiophene) (PEDOT)-inorganic composites. However, due to limited solubility and unmatched oxidation potentials, most oxidants only produce powders or porous materials. To obtain high-quality films with improved homogeneity and controllable particle sizes, the oxidants should be adaptable to high-standard PEDOT film fabrication techniques such as vapor phase polymerization (VPP). In this work, we discovered for the first time a nonferric metal salt suitable for the VPP process. With the addition of an Fe(III) salt to stabilize the reaction and adjust the oxidant ratio, micron-thick antibacterial S-PEDOT-Ag quantum dot (QD) composite films with tunable Ag wt% can be synthesized in one facile step. With a low Ag loading of ~0.2 wt%, the film exhibited an optimized power factor of 63.1 μW/mK2, which is among the highest values thus far reported for PEDOT-metal composites. Increase of the Ag(I) concentration in the precursor to a certain level may lead to minor decomposition of the polymer followed by the formation of Ag2S particles.

Design, synthesis, structure, and stability of novel multi-principal element (Ti,Zr,Hf,W)C ceramic with a miscibility gap

Here we design a novel multi-principal element carbide system (Ti,Zr,Hf,W)C with a miscibility gap using computational tools and report on the formation of a single-phase (Ti,Zr,Hf,W)C after spark plasma sintering. The (Ti,Zr,Hf,W)C shows high nanohardness (32.7 GPa) and fracture toughness (5 MPa·m1/2). Aging studies at 1350 °C for 100 h show that the single-phase carbide solid solution is quite stable even though this temperature is within the predicted miscibility gap of the system. Detailed electron microscopy characterization shows that phase separation has initiated with minor decomposition after aging by forming rock-salt (Ti,W)C- and (Zr,Hf)C-rich phases as well as hexagonal WC precipitates. We show that the (Ti,W)C- and (Zr,Hf)C-rich phases form a lamellar structure upon aging and the interlamellar spacing is considerably coarser than what has been previously found for the binary (Ti,Zr)C system. The decomposition kinetics, on the other hand, is sluggish due to the reduced driving force for phase decomposition.

Substituent Effects on Thermal and Mechanical Properties of Resorcinol‐Based Semiaromatic Polyesters

AbstractRecently biobased plastics draw attention as eco‐friendly materials, and it is important to study the effects of substituents, which are popularly found in natural products, on the characteristics of the resulted polymers. In this study, twelve resorcinol‐based semiaromatic polyesters are successfully synthesized using four types of resorcinol derivatives (resorcinol, 2‐methylresorcinol, 5‐methylresorcinol, and 2,5‐dimethylresorcinol) and three types of dicarboxylic acids (glutaric acid, adipic acid, and pimelic acid) to investigate the effect of methylation at the 2‐ and 5‐positions in resorcinol. Glass‐transition temperature of the polyesters is located from ‐3.1 to 37.9 °C, and rises with increasing the number of methyl groups in a resorcinol unit. Crystallinity of the polyesters decreases by methylation to a resorcinol unit, except the polyester from 2‐methylresorcinol and pimelic acid. The mechanical properties of the solvent‐cast films for the polyesters are tunable by the site and number of methyl groups in a resorcinol unit. The major thermal degradation of the polyesters is observed above 300 °C, and the minor thermal decomposition appears between 100 and 200 °C for the polyesters without the resorcinol methylated at the 2‐position and pimelic acid unit.

Kinetics of isopropanol decomposition and reaction with H atoms from shock tube experiments and rate constant optimization using the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE)

AbstractWe have used the single‐pulse shock tube technique with postshock GC/MS product analysis to investigate the mechanism and kinetics of the unimolecular decomposition of isopropanol, a potential biofuel, and of its reaction with H atoms at 918‐1212 K and 183‐484 kPa. Experiments employed dilute mixtures in argon of isopropanol, a radical scavenger, and, for H‐atom studies, two different thermal precursors of H. Without an added H source, isopropanol decomposes in our studies predominantly by molecular dehydration. Added H atoms significantly augment decomposition, mainly by abstraction of the tertiary and primary hydrogens, reactions that, respectively, lead to acetone and propene as stable organic products. Traces of acetaldehyde were observed in some experiments above ≈ 1100 K and establish branching limits for minor decomposition pathways. To quantitatively account for secondary chemistry and optimize rate constants of interest, we employed the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE) to carry out a unified analysis of all datasets using a chemical model–based originally on JetSurF 2.0. We find: k(isopropanol → propene + H2O) = 10(13.87 ± 0.69) exp(−(33 099 ± 979) K/ T) s−1 at 979‐1212 K and 286‐484 kPa, with a factor of two uncertainty (2σ), including systematic errors. For H atom reactions, optimization yields: k(H + isopropanol → H2 + p‐C3H6OH) = 10(6.25 ± 0.42) T2.54 exp(−(3993 ± 1028) K /T) cm3 mol−1 s−1 and k(H + isopropanol → H2 + t‐C3H6OH) = 10(5.83 ± 0.37) T2.40 exp(−(1507 ± 957) K /T) cm3 mol−1 s−1 at 918‐1142 K and 183‐323 kPa. We compare our measured rate constants with estimates used in current combustion models and discuss how hydrocarbon functionalization with an OH group affects H abstraction rates.

A promising strategy for bone fracture healing using spark plasma sintered substituted bioceramics

A low-temperature strain-induced chemical reaction and spark plasma sintering (SPS) were employed, for the first time, to prepare a consolidated form of the silver-doped hydroxyapatite (Ag-HA) as a potential biomaterial for bone fracture healing. In a quick sintering segment, Ag-HA was uniformly consolidated, while sustaining its stability. The XRD patterns showed a minor decomposition at 950 °C and some alterations wererecorded in the structural characteristics. The microhardness of the compacted specimens increased from 613 HV for pure HA to 637 HV for the doped sample.

Aliphatic polycarbonates derived from epoxides and CO2: A comparative study of poly(cyclohexene carbonate) and poly(limonene carbonate)

The ring-opening copolymerization (ROCOP) of epoxides and CO2 provides an alternative approach towards polycarbonates and due to their aliphatic nature, they represent an interesting alternative to bisphenol-A based polycarbonates. A Lewis acidic β-diiminate (BDI)CF3-Zn-(SiMe3)2 complex 1 is used in the ROCOP of CO2 with cyclohexene oxide (CHO) and limonene oxide (LO), respectively. The knowledge gained from polymerizations monitored via in situ IR spectroscopy was used to upscale the reactions to a 1 L reactor. The two products poly(cyclohexene carbonate) (PCHC) and poly(limonene carbonate) (PLC) were then characterized via thermal analysis, a multiaxial pressure test, and dynamic mechanical analysis and compared with commercial polymers. While PCHC and PLC were both thermally stable at 150 °C for 20 min and only minor decomposition occurred at 180 °C, PLC is prone to cross-linking at elevated temperatures. This could be prevented by hydrogenation of the double bond or by the addition of an antioxidant. In the mechanical performance, the aliphatic polymers ranged between the highly impact resistant Durabio® and the brittle PMMA but broke without a splintering of the material. Overall, this study enabled a classification of CO2-based polycarbonates, especially of the novel PLC. Additionally, complex 1 was active in the terpolymerization of CHO, LO, and CO2. The formation of an actual terpolymer was confirmed via aliquot gel-permeation chromatography and diffusion-ordered NMR spectroscopy. High-pressure NMR techniques reveal an interesting kinetic feature. CHO gets copolymerized with CO2 exclusively, and LO incorporation only starts when CHO is fully consumed.

Formation of formaldehyde as an artifact peak in head space GC analysis resulting from decomposition of sample diluent DMSO: A GC-MS investigation with deuterated DMSO

During our method development for residual formaldehyde detection in a drug substance, unusually high levels of formaldehyde were detected when using a mixed solvent of EtOH/DMSO (4:1, v/v) as sample diluent in headspace GC analysis (HS-GC). Initial investigation found that formaldehyde is used in the preparation for one of the starting materials of the drug substance. Nevertheless, there is neither other source of formaldehyde in the manufacturing process of the drug substance, nor would formaldehyde be generated during the process. In the ensuing root cause investigation, it was found that once the solvent DMSO is replaced by other solvent [e.g., N,N-dimethylformamide (DMF)], while keeping other method parameters unchanged in the HS-GC analysis, the level of formaldehyde in the same batch of the drug substance became undetectable (LOD: 3 ppm). All the evidence suggested that the observed formaldehyde in the HS-GC analysis might be due to the decomposition of DMSO, which could be facilitated by the presence of this particular drug substance. In other words, the presence of the drug substance (in the form of HCl salt) would cause a minor decomposition of DMSO to produce formaldehyde. To prove this hypothesis, a GC–MS experiment of the drug substance was conducted in which deuterated DMSO (DMSO-d6) was used in place of regular DMSO; the expected deuterated derivatization product, i.e., diethoxymethane-d2 (C2H5OCD2OC2H5), was observed in the HS-GC–MS analysis. Therefore, it became clear that this drug substance facilitates the minor decomposition of DMSO in the HS-GC analysis. In such a case, formaldehyde is an artifact peak, or ghost peak, rather than a true impurity of the drug substance. The false positive results of formaldehyde were also found in other four compounds (three drug substances and one reagent) which are all in the form of HCl or HBr salts, suggesting that generation of formaldehyde from DMSO could be a widely occurred phenomenon in HS-GC analysis of alkyl amines in the form of HCl or HBr salts, when DMSO-containing diluents are used during sample preparation.

Necessary and sufficient conditions for lossless negative imaginary systems

This paper studies some useful properties of lossless negative imaginary transfer matrices for both continuous-time and discrete-time systems. Necessary and sufficient conditions are established for lossless negative imaginary systems both in frequency domain and state-space realization. Meanwhile, a minor decomposition method for lossless negative imaginary systems is proposed in terms of a partial-fraction expansion. This method is important for developing non-proper lossless negative imaginary theory in this paper by allowing poles at the origin and infinity. Two new relationships between lossless positive real and lossless negative imaginary systems are consequently established. According to these new established relationships, a generalized continuous-time lossless negative imaginary lemma and a different version of discrete-time lossless negative imaginary lemma are developed in terms of a minimal state-space realization. Several examples are provided to illustrate the main results.

Site- and species-specific hydrolysis rates of cocaine

The hydroxide-catalyzed non-enzymatic hydrolysis of cocaine is quantified in terms of ten site- and species-specific rate constants in connection with also ten site- and species-specific acid-base equilibrium constants, comprising all the twelve coexisting species in solution. This characterization involves the major and minor decomposition pathways via benzoylecgonine and ecgonine methyl ester, respectively, leading to ecgonine, the final product. Hydrolysis has been found to be 10–330 times faster at site 2 than at site 3, depending on the ionization status of the amino moiety and the rest of the molecule. Nitrogen protonation accelerates the hydrolyses approximately ten times both at site 2 and site 3.

Downstream processing of hyperforin from Hypericum perforatum root cultures

Hyperforin is a major metabolite of the medicinal plant Hypericum perforatum (St. John’s Wort) and has recently been found in hormone induced root cultures. The objective of this study is to identify a downstream process for the production of a hyperforin-rich extract with maximum extraction efficiency and minimal decomposition. The maximum extraction time was found to be 60min. The comparison of two equipment concepts for the extraction and solvent evaporation was performed employing two different solvents. While the rotary mixer showed better results for the extraction efficiency than a stirred vessel, the latter set-up was able to handle larger volumes but did not meet all process requirements. For the evaporation the prompt evaporation of the extraction agent using nitrogen stripping led to minor decomposition. In a 5L stirred vessel, the highest specific extraction of hyperforin was 4.3mg hyperforin/g dry weight bio material. Parameters for the equipment design for extraction and solvent evaporation were determined based on the experimental data.

Origins of Regioselectivity in the Fischer Indole Synthesis of a Selective Androgen Receptor Modulator.

The selective androgen receptor modulator, (S)-(7-cyano-4-(pyridin-2-ylmethyl)-1,2,3,4-tetrahydrocyclopenta[b]indol-2-yl)carbamic acid isopropyl ester, LY2452473, is a promising treatment of side effects of prostate cancer therapies. An acid-catalyzed Fischer indolization is a central step in its synthesis. The reaction leads to only one of the two possible indole regioisomers, along with minor decomposition products. Computations show that the formation of the observed indole is most favored energetically, while the potential pathway to the minor isomer leads instead to decomposition products. The disfavored [3,3]-sigmatropic rearrangement, which would produce the unobserved indole product, is destabilized by the electron-withdrawing phthalimide substituent. The most favored [3,3]-sigmatropic rearrangement transition state is bimodal, leading to two reaction intermediates from one transition state, which is confirmed by molecular dynamics simulations. Both intermediates can lead to the observed indole product, albeit through different mechanisms.

Thermal degradation of random copolyesters based on 1,4-butanediol, terepthalic acid and different aliphatic dicarboxylic acids

Thermal stability and degradation kinetics have been studied for a series of aliphatic-aromatic copolyesters where the terephthalate content was varied between 30 mol-% and 70 mol-%. Succinate, adipate and sebacate were considered as the aliphatic dicarboxylate unit. All copolyesters were synthesized with a perfect random distribution by a thermal transesterification process from the corresponding homopolyesters.A complex degradation was deduced for all copolymers taking into account the increment of the activation energy with conversion. In fact, thermogravimetric curves showed a minor decomposition process in the low conversion region that was more significant for the succinate derivative and specifically for that having the lowest aromatic content. The sebacate derivative was characterized by the presence of an additional and minor decomposition process that took place at the highest conversion.All copolyesters were defined by a major decomposition process, which has similar values of activation energy regardless of the method used to calculate them (e.g. Kissinger, KAS or Friedman methodologies). This decomposition reaction followed a A4 Avrami-Erofeev mechanism when Coats-Redfern and Criado methodologies were applied. In summary, all the studied copolymers thermally decompose following a complex process but in all cases the main degradation step corresponds to a similar degradation mechanism.

Isoconversional approach for non-isothermal decomposition of un-irradiated and photon-irradiated 5-fluorouracil

Kinetic analysis for the non-isothermal decomposition of un-irradiated and photon-beam-irradiated 5-fluorouracil (5-FU) as anti-cancer drug, was carried out in static air. Thermal decomposition of 5-FU proceeds in two steps. One minor step in the temperature range of (270–283°C) followed by the major step in the temperature range of (285–360°C). The non-isothermal data for un-irradiated and photon-irradiated 5-FU were analyzed using linear (Tang) and non-linear (Vyazovkin) isoconversional methods. The results of the application of these free models on the present kinetic data showed quite a dependence of the activation energy on the extent of conversion. For un-irradiated 5-FU, the non-isothermal data analysis indicates that the decomposition is generally described by A3 and A4 modeles for the minor and major decomposition steps, respectively. For a photon-irradiated sample of 5-FU with total absorbed dose of 10Gy, the decomposition is controlled by A2 model throughout the coversion range. The activation energies calculated in case of photon-irradiated 5-FU were found to be lower compared to the values obtained from the thermal decomposition of the un-irradiated sample probably due to the formation of additional nucleation sites created by a photon-irradiation.The decomposition path was investigated by intrinsic reaction coordinate (IRC) at the B3LYP/6-311++G(d,p) level of DFT. Two transition states were involved in the process by homolytic rupture of NH bond and ring secession, respectively.