Influences of Bis-(2,6-Diisopropylphenyl) Carbodiimide on the Thermal Stability and Crystallization of Poly(P-Dioxanone)

The influences on the thermal degradation and crystallization behaviors of poly(p-dioxanone) (PPDO) were initially investigated by adding bis-(2,6-diisopropylphenyl) carbodiimide (labeled as St). It was found that the addition of St could significantly enhance the thermal stability and crystallizability of PPDO. The thermal decomposition temperature of PPDO increased with the increase of the amount of St added. The thermal decomposition activation energies of PPDO increased from 94.2 to 130.8 kJ mol^?1 in the case of 5 wt% St. The addition of St did not change the crystal structure of PPDO, while it increased the number of nucleation sites and improved the crystallizability of PPDO. The crystallization activation energies, calculated by the Kissinger method, for PPDO and PPDO/5 wt% St were ?111.4 and ?141.5 kJ mol^?1, respectively, confirming the crystallizability of PPDO was enhanced after the addition of St.     

Physical insights into the sonochemical degradation of recalcitrant organic pollutants with cavitation bubble dynamics

This paper tries to discern the mechanistic features of sonochemical degradation of recalcitrant organic pollutants using five model compounds, viz. phenol (Ph), chlorobenzene (CB), nitrobenzene (NB), p-nitrophenol (PNP) and 2,4-dichlorophenol (2,4-DCP). The sonochemical degradation of the pollutant can occur in three distinct pathways: hydroxylation by OH radicals produced from cavitation bubbles (either in the bubble–bulk interfacial region or in the bulk liquid medium), thermal decomposition in cavitation bubble and thermal decomposition at the bubble–liquid interfacial region. With the methodology of coupling experiments under different conditions (which alter the nature of the cavitation phenomena in the bulk liquid medium) with the simulations of radial motion of cavitation bubbles, we have tried to discern the relative contribution of each of the above pathway to overall degradation of the pollutant. Moreover, we have also tried to correlate the predominant degradation mechanism to the physico-chemical properties of the pollutant. The contribution of secondary factors such as probability of radical–pollutant interaction and extent of radical scavenging (or conservation) in the medium has also been identified. Simultaneous analysis of the trends in degradation with different experimental techniques and simulation results reveals interesting mechanistic features of sonochemical degradation of the model pollutants. The physical properties that determine the predominant degradation pathway are vapor pressure, solubility and hydrophobicity. Degradation of Ph occurs mainly by hydroxylation in bulk medium; degradation of CB occurs via thermal decomposition inside the bubble, degradation of PNP occurs via pyrolytic decomposition at bubble interface, while hydroxylation at bubble interface contributes to degradation of NB and 2,4-DCP.     

A study of the effect of gamma and laser irradiation on the thermal,optical and structural properties of CR-39 nuclear track detector

A comparative study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of the CR-39 diglycol carbonate solid state nuclear track detector has been carried out. Samples from CR-39 polymer were classified into two main groups: the first group was irradiated by gamma rays with doses at levels between 20 and 300 kGy, whereas the second group was exposed to infrared laser radiation with energy fluences at levels between 0.71 and 8.53 J/cm². Non-isothermal studies were carried out using thermogravimetry, differential thermogravimetry and differential thermal analysis to obtain activation energy of decomposition and transition temperatures for the non-irradiated and all irradiated CR-39 samples. In addition, optical and structural property studies were performed on non-irradiated and irradiated CR-39 samples using refractive index and X-ray diffraction measurements. Variation in the onset temperature of decomposition T _o, activation energy of decomposition E _a, melting temperature T _m, refractive index n and the mass fraction of the amorphous phase after gamma and laser irradiation were studied.

It was found that many changes in the thermal, optical and structural properties of the CR-39 polymer could be produced by gamma irradiation via degradation and cross-linking mechanisms. Also, the gamma dose has an advantage of increasing the correlation between thermal stability of the CR-39 polymer and bond formation created by the ionizing effect of gamma radiation. On the other hand, higher laser-energy fluences in the range 4.27–8.53 J/cm² decrease the melting temperature of the CR-39 polymer and this is most suitable for applications requiring molding of the polymer at lower temperatures.     

The thermal decomposition of mono-, di-, and tripotassium salts of trinitrophloroglucinol

The kinetics of the thermal decomposition of mono-, di-, and tripotassium salts of trinitrophloroglucinol (TNPG) was studied in the solid phase by the manometric method at m/V from 1 × 10^?4 to 15 × 10^?4 g/cm³ over the temperature ranges 125–150°C (K₁TNPG), 200–230°C (K₂ TNPG), and 200–250°C (K₃ TNPG). All the compounds decomposed according to the topochemical mechanism: there was an induction period, after which the rate of gas release was maximum. This rate then gradually decreased. The second decomposition stage was observed for K₁TNPG as the temperature increased to 200–250°C. The special features of changes in the rate of the process during transformation and the influence of the degree of vessel filling with a substance, particle size, and temperature on the kinetics of decomposition were studied. The kinetic results and composition of gaseous products and some condensed decomposition products lead to certain conclusions concerning the mechanism of the chemical transformations.     

A Kinetic Study on the Thermal Degradation of Polypropylene/Attapulgite Nanocomposites

In this work, a polypropylene (PP)/attapulgite nanocomposite was prepared via melt blending using a novel organically modified attapulgite (OATP). The thermal stability of PP/clay nanocomposites compared to pure PP was examined in nitrogen using a kinetic analysis. The kinetic parameters, including reaction order and activation energy (A and E _a) of the degradation process were determined by applying the Flynn‐Wall‐Ozawa method using derivative thermogravimetric (DTG) curves. At the same time, the effect of organic attapulgite on thermal decomposition of polypropylene matrix was analyzed. As a result, PP/OATP nanocomposites have slightly higher degradation temperature than that of the pure PP. The values of the reaction order of PP and PP/OATP nanocomposites are close to 1 in the nonisothermal degradation process. The activation energies of PP/OATP nanocomposites also increase slightly compared to the pure PP, thus it is suggested that the org‐attapulgite has little effect on the thermal stability of the pure PP.     

Prediction of minimum water amount to stop thermal decomposition of forest fuel

Presented are results of experimental studies of the heat transfer processes in suppression of thermal decomposition of typical forest fuels (FFs) (spruce needles, birch leaves, aspen twigs, or amixture thereof) due to the effect of aerosol water flow (drop radii: 0.01–0.12 mm; concentration: 3.8 · 10^?5 m³ drop/m³ of gas). The experiments have been carried out with FF samples in the form of cylinders of a thickness of 40–100 mm and a diameter of 20–150 mm. The times required to stop the thermal decomposition of FF have been found, as well as amounts of water necessary to lower in a given time the temperature in a layer of material to the point of decomposition beginning. A dimensionless complex has been derived for prediction of water spraying parameters (amount and time of supply) that ensure sustainable termination of FF decomposition within a specified time interval.     

Characteristics of the initiation of the explosive decomposition of PETN by the second-harmonic pulsed radiation of a neodymium laser

The critical fluence of the initiation of the explosive decomposition of pentaerythritol tetranitrate (PETN) by the second harmonic of a neodymium laser (532 nm) is found to be 12.3 J/cm². It is shown that, under these conditions, the nonlinear two-photon absorption of light takes place. The critical fluence of the initiation of PETN explosive decomposition in the two-photon absorption mode is calculated within the framework of the thermal explosion model (14.7 J/cm²), which indicates that the thermal mechanism of explosive decomposition is operative under these conditions.     

Proton-induced changes in Bayfol CR 1-4 nuclear track detector

Samples from the polymeric material Bayfol CR 1-4 have been exposed to 1 MeV protons with fluencies in the range 10¹¹–10¹⁴ ions/cm ². The resultant effect of proton irradiation on the thermal properties of Bayfol CR 1-4 has been investigated using thermo-gravimetric analysis (TGA). The onset temperature of decomposition T ₀ and activation energy of thermal decomposition E _a were calculated, results indicated that the Bayfol detector decomposes in one weight loss stage. In addition, the structural modifications in the proton-irradiated Bayfol samples have been studied as a function of fluence using X-ray diffraction and intrinsic viscosity of the liquid samples. Furthermore, the refractive index was measured for the non-irradiated and irradiated Bayfol samples. The results indicated that the degradation is the dominant mechanism in the fluence range 1×10¹¹–5×10¹⁴ ions/cm ². These results have been compared with those obtained in our previous work for Bayfol CR 6-2.     

Lateral growth rates in laser CVD of microstructures

Lateral growth rates of Ni spots deposited on absorbing substrates by decomposition of Ni(CO)₄ with visible Kr⁺ laser light have been measured. The experimental data are consistent with the calculated temperature distributions. The mechanism of decomposition is thermal with an apparent chemical activation energy of 22±3 kcal/mole for the temperature range 350 KT500 K.     

Influence of Ca2+ or Na+ extraframework cations on the thermal dehydration and related kinetic performance of LSX zeolite

Nitrogen adsorption performances of low-silica type X zeolites (LSX) containing Na⁺ or Ca²⁺ ions were studied and compared with Li⁺ ion, and their structural and thermal properties were investigated using various characterizations (XRD, TG-DTG, BET, XPS, SEM, TEM, and EDX with elemental mapping techniques). The kinetics of their thermal dehydration and decomposition was studied using thermogravimetry at three rates (5, 10, and 15 K/min) of linear increase of temperature under non-isothermal heating. Two model free procedures named, Kissinger, and Flynn–Wall–Ozawa (iso-conversional) and one model fitting method called Coats–Redfern based on single TG curves, as well as 41 mechanism functions were used. The kinetic parameters (apparent activation energy E, pre-exponential factor A and model) of the three phases for each sample obtained from the non-isothermal methods were then compared with the results from iso-conversional methods this showed that they strongly depend on the selection of appropriate mechanism function and the corresponding kinetic model from the perspective of crystal structure used. The results demonstrated that the E value obtained at low temperature was lower than that at high temperature, implying that the dehydration process of physisorbed water belongs to diffusion-based control, while decomposition of bonded water (chemisorbed) belongs to kinetic-based control at high temperature. These comparisons allow us to underline the strong effect of cations in association with water and their distribution in the micropores of LSX on the N₂ adsorption performance.     

Effects of Molecular Weight on Thermal Degradation of Poly(α-methyl styrene) in Nitrogen

The effects of molecular weight on the thermal degradation behavior of poly(α-methyl styrene) (PAMS) was investigated by pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) and thermogravimetric analysis (TGA). The Py-GC/MS analysis results showed that the degradation of PAMS with different molecular weights in nitrogen produced only the monomer, alpha-methylstyrene. The TGA results showed a pronounced reduction in the decomposition temperature with increasing molecular weight. The degradation kinetic parameters, calculated by the Kissinger and the Coats–Redfern methods, further revealed that the activation energy and the pre-exponential factor decreased with increasing molecular weight. Most importantly, the degradation order of the PAMS in nitrogen remained around 1, independent of the molecular weight, suggesting the maintenance of the depolymerization mechanism. All the above results provided an insight into the effects of molecular weight on the thermal degradation behavior of PAMS.     

Investigation of the degradation mechanisms in BaMgAl10O17:Eu2+ phosphor: on the influence of thermal process on operational durability

The thermal and operational degradation in optical property of a europium-doped barium magnesium aluminate (BaMgAl₁₀O₁₇:Eu²⁺, BAM) phosphor was studied. BAM was heat-treated at 500°C under various conditions to determine the mechanism of thermal degradation. Operational degradation tests were then performed under a discharging Xe/Ne mixed gas to study the influence of thermal history on operational degradation. It was found that the atmosphere during thermal processing was the major factor affecting not only the thermal degradation, but also the operational degradation. The sample heat-treated under a reducing atmosphere showed enhanced stability during operation.     

The role of electric current in the formation of white-etching-cracks

ABSTRACT

Material failure by white-etching-cracks (WECs) can cause enormous economic costs. The formation of WECs emerges from the decomposition of the original, usually cementite-containing, microstructure. As small amounts of electric current can trigger this failure mechanism, we investigate the contribution of electric current to cementite decomposition. We applied ～700 A/cm² for two weeks at 60°C to a pearlitic Fe-0.74C (wt%) specimen. The comparison of the microstructure before and after showed no differences. Theoretical considerations support the conclusion that at this low temperature such electric current densities cannot directly cause cementite decomposition. Electric current could play an indirect role in the formation of WECs, however, by generating hydrogen from the lubricant which is known to accelerate WECs formation.     

Thermal decomposition of 2,4,6-triazidopyridine

The thermal decomposition of 2,4,6-triazidopyridine in the melt is studied using thermogravimetry, manometry, mass spectrometry, and IR spectroscopy. In the temperature range of 120–160°C, the process obeys the first-order kinetic law, being described by the Arrhenius equation k [s^–1] = 10^{12.8 ± 0.4}exp[–(31200 ± 1500)]/RT with values of the parameters typical of the thermal decomposition of aromatic and heterocyclic azides. The reaction produces nitrogen, as the only gaseous product. Unlike the other heterocyclic azides, the decomposition of which is characterized by anomalously high values of the Arrhenius parameters, the thermal decomposition of 2,4,6-triazidopyridine yields a condensed product having a system of polyconjugated bonds with higher force characteristics. It is concluded that the decomposition of 2,4,6-triazidopyridine proceeds by a mechanism in which the rate-limiting step is the dissociation of the nitrogen molecule from the azide group to form a nitrene.     

Fourier transform infrared spectroscopy to detect thermal degradation of vegetable and chrome-tanned leather

Abstract

The present experimental study determined the thermal degradation stages for vegetable and chrome-tanned leathers (goat and sheep) at 90, 100, and 130?°C by using Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis. Infrared spectra revealed that a temperature of 90?°C affected the adsorbed water band at 3400?cm^?1. Moreover, this temperature slightly reduced the vibrations of amide II and amid III (1340?cm^?1) confirming the preliminary decomposition of protein folds, but it is worth noting that the aliphatic side chains remained stable at this stage of aging. At 100?°C, there was a sharp rupturing in the phenolic-OH bond and side-by-side N–H vibrations decreased dramatically. The peak decomposition occurred at 130?°C, where the amide I and amide III intensities significantly increased, which can be considered indicative of protein unfolding. Those changes are substantiation of protein denaturation. Thermal analysis demonstrated that thermal aging significantly reduced the required temperature for the process of oxidation. The oxidation occurred at 217?°C in goat sample aged at 90?°C. Nevertheless, the reference sample suffered from oxidation at about 220?°C, while with increasing aging temperatures (at 100 and 130?°C), endothermic reactions were observed. Such reactions are usually associated with protein denaturation.     

Preparation,Characterization and Thermal Decomposition of Polyimides with Main Chain Containing Cycloaliphatic Units

Two polyimides with main chain containing cycloaliphatic units were synthesized by conventional two‐step polycondensation of two diamines, 1,4‐bis (4‐aminophenoxymethylene) cyclohexane (BAMC) and 1,4‐bis (4‐aminobenzoyoloxymethyl) cyclohexane (BAZMC), with a dianhydride 3,3′, 4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), respectively. The resulting polyimides showed exceptional thermal properties with glass transition temperatures of 212 and 178°C, and temperature for 5% weight loss of 461 and 421°C in nitrogen, respectively. Meanwhile, thermogravimetry coupled to Fourier transform infrared spectrometry (TG/FT‐IR) was used to study the thermal degradation behavior of the resulting polyimides. It was found that the thermal decomposition occurred by a double‐stage process; the major evolved products from the nonoxidative thermal degradation were hydrocarbon, CO, CO₂, H₂O, and aromatic compounds.     

Preparation of the nickel foam/Ni-Ce-Co-O film electrode by thermal decomposition for oxygen evolution reaction

The Ni-Ce-Co-O film on nickel foam was prepared by thermal decomposition of acetates. The electrochemical activity of the film was affected by the temperature of thermal decomposition. Cerium ions introduced into the oxide film could increase the surface area and improve the oxygen evolution reaction (OER) activity of the electrode. Compared with thermal decomposition of nitrates, the OER activity of the film prepared with acetates was higher. When the nickel foam/Ni-Ce-Co-O film electrode prepared with acetates was used as the anode, in 30% KOH solution (88 ± 2 °C) at the current density of 4000 A/m², the cell voltage was 250 mV lower than that of the nickel foam anode. Furthermore, the film electrode exhibited good stability.     

A thermal and electrochemical properties research on gel polymer electrolyte membrane of lithium ion battery

N-methyl-N-propyl-piperidin-bis(trifluoromethylsulfonyl)imide/bis(trifluoromethylsulfonyl) imide lithium base/polymethyl methacrylate(PP₁₃TFSI/LiTFSI/PMMA) gel polymer electrolyte (GPE) membrane was prepared by in situ polymerization. The physical and chemical properties were comprehensively discussed. The decomposition characteristics were emphasized by thermogravimetric (TG-DTG) method in the nitrogen atmosphere at the different heating rates of 5, 10, 15 and 20 °C min⁻¹, respectively. The activation energy was calculated with the iso-conversional methods of Ozawa and Kissinger, Friedman, respectively, and the Coats-Redfern methods were adopted to employ the detailed mechanism of the electrolyte membrane. The equation f(α)=3/2[(1−α)^1/3−1] was quite an appropriate kinetic mechanisms to describe the thermal decomposition process with an activation energy (E_α) of 184 kJ/mol and a pre-exponential factor (A) of 1.894×10¹¹ were obtained.