Thermal Decomposition Process Research Articles

Exploring microfine magnesite based on thermal decomposition and sintering kinetics: A new direction in the one-step preparation of high-density sintered magnesia

The thermal decomposition and sintering kinetics of microfine magnesite were investigated to inaugurate a new One-step process for preparing high-density sintered magnesia. The optimal parameters for the discharging particle size of magnesite through ball milling were determined using an orthogonal experiment and Three-Way Measures ANOVA. The model for the thermal decomposition process of microfine magnesite was established through TGA-DSC and nonlinear regression analysis. Meanwhile, by describing the sintering process of microfine magnesite in detail through microstructure and CTE, the kinetic mechanisms of grain growth at different sintering stages were obtained. The results revealed that increasing the ratio of ball to powder can quickly obtain microfine magnesite which the bulk density reaches 3.45 g·cm−3 after One-step sintering. The thermal decomposition process required an activation energy of only 124.98 kJ·mol−1, which is much lower than existing technology and followed the Two-dimensional phase boundary reaction mechanism R2. Additionally, the densification process was dominated alternatively by grain boundary diffusion and volume diffusion. This paper provided a detailed theoretical basis and leads a new direction in the One-step preparation of high-density sintered magnesia.

Preparation of metal–organic framework-199 (Cu) and their effects on catalytic decomposition of hexahydro-1,3,5-trinitro-s-triazine

In this study, a series of metal–organic framework-199 (MOF-199) products were prepared with copper (Cu) as the metal center and trimesic acid as the organic ligand. The morphological changes of MOF-199 under different preparation conditions and its application in the catalytic thermal decomposition of hexahydro-1,3,5-trinitro-s-triazine (RDX) were studied. The morphological changes of MOF-199 were compared by scanning electron microscopy (SEM), the crystal structures of MOF-199 were analyzed by X-ray diffraction and the effects of MOF-199 with different morphological characteristics on the thermal decomposition behavior of RDX were studied by differential scanning calorimetry. The results showed that MOF-199 with different morphologies could effectively adjust the thermal decomposition process of RDX and reduce the decomposition peak temperature of RDX, and the catalytic effect of MOF-199 was different due to different crystal surfaces exposed. Among them, (110) was a highly active crystal plane with a high catalytic activity. In addition to the crystal plane structure, the defects on the surface of MOF-199 would also affect its catalytic performance. This study provides some theoretical support for the catalytic mechanism of MOFs in the thermal decomposition of nitro compounds.

Unlocking biosolid pyrolysis: Towards tailored biochar with different surface properties

To develop a thorough understanding of the thermal decomposition process of biosolids and the qualities of biosolid-derived biochar, this study performs a thermogravimetric analysis (TGA) of biosolids and examines the properties of biosolid-derived biochar produced from varying temperatures of pyrolysis. The pyrolysis of biosolid is conducted under varying heating rates (10, 15, 20 and 25 °C/min) until reaching the maximum temperature of 900 °C. The kinetic triplet (kinetic model, activation energy, and frequency factor) at the corresponding conversion point is determined by analysing the TGA results of the biosolids. The thermal degradation of hydrated compounds shows activation energies ranging from 80 to 100 kJ/mol, whereas the thermal decomposition of organic matter in biosolids exhibits activation energies ranging from 120 to 497 kJ/mol. As the temperature increases, the thermal reactions transition from simple surface reactions with frequency factors below 109 s-1 to more complex reactions with frequency factors above 109 s-1. The distributed activation energy model (DAEM) is established using the approximated temperature function and the activation energy distribution functions. The DAEM shows the mean activation energies of 93–128 kJ/mol, 279–287 kJ/mol and 359–377 kJ/mol for activation energy distribution peaks. The standard deviations of the mean activation energies are 30–64 kJ/mol, 23–30 kJ/mol and 23–41 kJ/mol, respectively. As the pyrolysis temperature is raised from 700 °C to 900 °C, both the specific surface area and micropore volume of biosolid-derived biochar increase, from 48.25 m2/g to 65.74 m2/g and 0.0313 cm3/g to 0.0369 cm3/g, respectively. The findings of this study demonstrate biosolid pyrolysis kinetics, which is essential for establishing a pyrolysis facility for biosolid management and producing biosolid-derived biochar with varying qualities.

Thermal Decomposition Mechanism of P(DAC-AM) with Serial Cationicity and Intrinsic Viscosity.

The thermal decomposition of the thermodynamic, kinetic and mechanisms of copolymer P(DAC-AM) samples with serial cationicity and intrinsic viscosity ([η]), and the control samples of homopolymer PAM and PDAC, were studied and analyzed using TG, DSC, FTIR. The results of the thermal decomposition thermodynamics confirmed that the thermal decomposition processes of the serial P(DAC-AM) samples and the two control samples could be divided into two stages. It was found that the processes of the copolymer P(DAC-AM) samples were not a simple superposition of those of homopolymers, whose monomers had composed the unit structures of the copolymer, but there were interactions between the two suspension groups. The results of thermal decomposition kinetics showed that the apparent activation energy (E) of the thermal decomposition process of all polymer samples had different varying trends in the terms of weight-loss rate (α). The reaction order (n) of the thermal decomposition of P(DAC-AM) in Stage I and II was close to 1, but in the former and the latter it tended to be 2 and 0.5, respectively. Finally, the thermal decomposition mechanism of copolymer P(DAC-AM) samples was discussed. The above research could not only fill in the knowledge vacancy of the thermal decomposition of the thermodynamic, kinetic and mechanisms of P(DAC-AM), but could also lay a foundation for the study of thermal decomposition mechanisms of the other types of polymers, including cationic polymers.

An optimisation study for leaching synthetic scheelite in H2SO4 and H2O2 solution

ABSTRACT Tungsten production primarily relies on scheelite, a secondary resource due to its complex ore composition and lower grade compared to high-grade wolframite. Synthetic scheelite gains significance for its low impurity content and accessibility in ongoing laboratory-based investigations. Recent advancements offer a feasible environment-friendly leaching method using a mixed solution of H2SO4 and H2O2 under normal pressure and moderate temperatures. However, comprehensive research on this novel method is lacking, emphasising the need for collaborative exploration and operational optimisation. The present work is to provide insights and improvements in reagent usage to promote economic and environmental sustainability. A detailed investigation into the thermal decomposition process was also conducted without compromising leaching efficiency. The findings suggest the potential for eco-friendly lixivium recycling with reduced levels of chemicals, decreasing operational costs. Notably, optimising the thermal decomposition duration to 6 hours at an L/S (mL/g) ratio of 10 enhances H2WO4 crystallization. Furthermore, experiments without H2SO4 supplementation highlight the system's optimisation potential. Finally, the leaching process was optimised by decreasing H2SO4 concentration to 1 mol/L from 3 mol/L, increasing the temperature to 60°C, and extending the leaching duration to 120 minutes. This leads to a cost-effective synthetic scheelite leaching process with environmental benefits.

Investigations of the carbonization process of hybrid polymer microspheres using the TGA-EGA method: assessment of the impact of sulphanilic acid on the process

AbstractThe TGA-EGA technique was used to study the influence of sulphanilic acid (SA) on the carbonisation process of the hybrid terpolymeric precursors composed of methacrylamide, divinylbenzene, and trimethoxyvinylsilane. The pristine polymers were impregnated with saturated solution of SA, dried, and carbonized at 600 °C under N2 atmosphere. The characteristic properties of both the pristine hybrid polymers and the resulting carbons were based on FTIR, Raman, and PXRD analyses, which revealed the materials were composed of amorphous polymeric or carbon phase interpenetrated by silica/silicate disordered network. The porosimetric analysis showed the resulted carbons possessed homogeneous supermicropores with the average pore width of 0.7 nm and reduced number of mesopores compared to pristine precursors. From the TGA results, it was followed that impregnated polymers decomposed in two stages, instead of one like pristine precursors did. Moreover, IDT of impregnated polymers was reduced by about 100 °C, and their Tmax was increased by 2–5.5 °C. Their decomposition proceeded slower by 22–37% that caused increase in efficiency of the process by 10–48%. The EGA showed the decomposition of the impregnated precursors started from the degradation of the amide groups, then SA destruction took place, followed by further decomposition of the polymer. The studies led to the conclusion that SA had the protective effect on the surface of the carbonized polymers. During impregnation and thermal treatment, SA produced a deposit in pores of the precursors. This resulted in narrowing of the pore width, delaying and slowing down the polymer thermal decomposition process, as well as increasing its efficiency.

Synthesis of Cu-MOF-derived complex copper–chromium oxides and their catalytic study on the thermal decomposition of ammonium perchlorate

In this work, a series of complex copper-chromium oxides were prepared by adjusting the molar ratio of Cr3+/Cu2+ using MOF-199 as a template. X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure, microscopic morphology and valence information of the samples. The specific surface area of the sample was estimated by the Brunauer-Emmett-Teller method (BET), and the pore size parameters of the sample were obtained by using the Barrett-Joyner-Halenda (BJH) model. The effect of the samples on the thermal decomposition process of ammonium perchlorate (AP) was investigated by differential scanning calorimetry-thermogravimetric analysis. The results show that the copper and chromium oxides in the complex exhibit good catalytic effects. Among them, CuCr(0.8) had the best catalytic effect, reducing the peak pyrolysis temperature of AP by 95.7 °C, increasing the heat release by 817 J/g, and reducing the reaction activation energy by 62.4 kJ/mol. Real-time FTIR was used to characterize the gas products during the thermal decomposition of AP, and the gas products of AP with CuCr(0.8) catalyst were different from those of pure AP, which may also be the reason for the increase of AP heat release after adding CuCr(0.8) catalyst.

Experimental investigations of hydrogen iodide (HI) decomposition process for different catalysts and various temperature conditions

This article presents the results of experimental work carried out at the Institute of Power Engineering on the process of thermal decomposition of hydrogen iodide. This process is one of the three key steps taking place in sulfur-iodine (S-I) thermochemical hydrogen production technology. For this purpose, a laboratory test rig equipped with an electrically heated chemical reactor was constructed, enabling the study of hydrogen iodide decomposition under controlled conditions. The research was carried out using various catalytic substances, as well as different temperature conditions. The process of hydrogen iodide decomposition required keeping the temperature of the reactor above 300°C and continuous analysis of the concentration of hydrogen formed over time. The results of the study will make it possible to determine the kinetics of the hydrogen iodide decomposition reaction under selected conditions of the process, allowing for future optimization of the process with the use of numerical methods.

Study on laser ignition and combustion characteristics of micron-sized aluminum and Al-Mg alloys particles

In response to the problems of easy sintering and long ignition delay time of micron aluminum in the combustion of aluminum-containing propellants, choose the way to add magnesium to metal aluminum to construct an alloy system, through boiling, micro-explosions are generated during the ignition and combustion process to weaken the sintering behavior and shorten the ignition delay time of aluminum. Selecting aluminum and Al-Mg alloy powder fuel with a particle diameter of about 10 μm as the research object, a set of individual-particle fuel laser ignition and microscopic high-speed imaging experimental devices was built that can observe the whole process of ignition and combustion of micron-sized fuel. Thermal analysis was used to detect and characterize the thermal decomposition process of micron-sized aluminum and Al-Mg alloy powders; combined with the results of scanning electron microscopy, the difference in ignition performance of micron-sized individual particle aluminum and Al-Mg alloys was studied. Experiments have found that, compared with aluminum, the initial oxidation temperature of Al-Mg alloys is lower and the combustion is more complete. However, the effect of adding magnesium to aluminum is only reflected before 900 °C. The ignition and combustion images and flame propagation laws of micron-sized single-particle aluminum and Al-Mg alloys were obtained. It was found that adding magnesium shortened the ignition delay time, and the combustion produced less residual.

Fabrication and characterization of Zn-hydroxy double salt-loaded composite: Antimicrobial and flame-retardancy properties

Herein, a novel versatile composite comprising Zn-hydroxy double salt (ZnHDS) and tannic acid (TA) fillers within a polyvinyl alcohol-polyethylene imine (PVA-PEI) mixed matrix (ZnHDS-TA@PVA-PEI) was fabricated and characterized. This composite exhibited dual functionality as an antimicrobial agent and a flame retardant. The composite exhibited significant antimicrobial activity against E. coli and S. aureus strains. The incorporation of ZnHDS into TA@PVA-PEI significantly enhanced its antimicrobial efficacy and flame-retardancy. Clearing zones for the ZnHDS-TA@PVA-PEI against E. coli and S. aureus with 3.8 % ZnHDS loading were obtained as 8.5 and 5.5 mm, respectively. The ZnHDS-TA@PVA-PEI, with a 3.8 % ZnHDS loading, required 18.52 kJ/mol of energy to initiate its thermal decomposition and absorbed a net energy of 41.40 J/g during the process. The maximum weight loss rates for ZnHDS, PVA-PEI, TA@PVA-PEI, and ZnHDS-TA@PVA-PEI were 0.50, 0.75, 0.99, and 0.85 %/°C, respectively. Water solubility tests demonstrated augmented resistance to water with increasing ZnHDS content. The introduction of ZnHDS into TA@PVA-PEI significantly improved the flame-retardancy, was slow to ignite, and self-extinguished within seconds. The thermal decomposition process, antimicrobial activity, and flame-retardancy mechanisms of the composites are discussed. These results, along with the affordability, biocompatibility, and eco-friendliness of ZnHDS, revealed its potential for multiple applications.

Electrical conductivity and thermal stability of polyaniline and water-soluble polymer nanocomposites

Electrically conductive composites with film-forming properties based on polyaniline (PANI), polyvinyl alcohol (PVA), and polymethacrylic acid (PMAA) were obtained. The composites were synthesized mechanochemically by mixing calculated amounts of PANI and PVA or PMAA. The electrical conductivity increases with an increase in the content of the conductive component in the composite up to a PANI–PVA ratio of 50 to 50. Further increase of PVA in the composite leads to a decrease in the specific electrical conductivity. Similar patterns are observed for PANI–PMAA composites. The study of the effect of temperature on the electrical conductivity of composites made it possible to determine the activation energy of charge transfer (Ea ). The numerical values of Ea lie in the range of 0.371 to 0.981 eV and depend on the ratio of PANI–PVA and PANI–PMAA polymers in the composites. The thermal decomposition of composites and starting components is complex. Several areas are observed on the mass change curves, which indicate a multi-stage thermal decomposition process.

Synthesis of graphene mesosponge using CaO nanoparticles formed from CaCO3

While graphene mesosponge (GMS) is a new type of mesoporous material with the potential for a variety of applications, its synthesis process requires costly templates such as Al2O3 and MgO nanoparticles. In this study, we present a new synthesis method for GMS, which achieves a high specific surface area of 1720 m2 g1 by employing calcium oxide (CaO) nanoparticles as templates. The CaO nanoparticles with an approximate diameter of 86 nm are formed through the thermal decomposition of calcium carbonate nanoparticles. However, the calcium carbonate nanoparticles contain a small amount of Mg (2 wt %), and the thermal decomposition process also yields impurities, including Mg. When the CaO nanoparticles, including the Mg-based impurities, are subjected to chemical vapor deposition, the CaO surface can be coated with a thin carbon layer, primarily consisting of single-layer graphene through the specific catalysis of the CaO surface in facilitating the CH4-to-C conversion reactions. However, at the same time, the presence of Mg-based impurities leads to the formation of low-crystalline carbons, which have a detrimental effect on the subsequent high-temperature annealing at 1800 °C, following the template removal process, resulting in an excessive number of edge sits in the GMS. We have found that the harmful low-crystalline carbons can be eliminated through heat treatment in air at 350 °C. By adopting such a removal process, high-quality GMS with a minimal number of edge sites can be produced.

Analytical Pyrolysis of Soluble Bio-Tar from Steam Pretreatment of Bamboo by Using TG-FTIR and Py-GC/MS.

Steam pretreatment at high temperatures enables fresh bamboo to possess antifungal and antiseptic properties. The process produces a large amount of wastewater that urgently needs to be recycled. Soluble bio-tars derived from wastewater under low-temperature (LTS-tar) and high-temperature (HTS-tar) steam pretreatments of moso bamboo were studied with a thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS). Thermogravimetric analysis showed that in the three stages of the thermal decomposition process, the final residue of the bamboo and HTS-tar had two main peaks of 0.88 wt% and 6.85 wt%. The LTS-tar had much more complicated thermal decomposition behavior, with six steps and a high residue yield of 23.86 wt%. A large quantity of CH4 was observed at the maximum mass loss rates of the bamboo and bio-tars. Acids, aldehydes, ketones, esters, and phenolic compounds were found in the pyrolysis products of the bamboo and soluble bio-tars. Both bio-tars contained carbohydrates and lignin fragments, but the LTS-tar under mild steam conditions had more saccharides and was much more sensitive to temperature. The lignin in the bamboo degraded under harsh steam conditions, resulting in high aromatic and polymeric features for the HTS-tar. The significant differences between LTS-tar and HTS-tar require different techniques to achieve the resource utilization of wastewater in the bamboo industry.

Sn-based precursors dependence for electrocatalytic degradation of organic pollutants on Ti/SnO2-Sb electrode

The utilization of SnO2-based coated electrodes prepared through thermal decomposition process for degrading organic pollutants is a prominent topic in the field of wastewater treatment. However, the impact of precursor salts on the structure and catalytic degradation activity of Sn oxide coatings still lacks research. This study examined the procedures for synthesizing SnO2 coatings by high-temperature oxidation of two common Sn chlorides with different valences. Through systematic characterization, it was revealed that the high boiling point of SnCl2 makes it less volatile during the high-temperature oxidation stage, allowing for maximum retention of Sn source on the substrate, thereby forming a dense and stable oxide coating structure (Ti/SnO2-Sb(II)). On the other hand, the low boiling point of SnCl4 makes it easily volatile during heating, resulting in a thin and loose structure coating (Ti/SnO2-Sb(IV)). Due to these factors that the electrical conductivity of Ti/SnO2-Sb(II) is significantly superior to Ti/SnO2-Sb(IV). Moreover, at 20 mA·cm−2, Ti/SnO2-Sb(II) can achieve almost complete decolorization of methylene Blue (MB) in just 40 minutes, while achieving the same decolorization rate with Ti/SnO2-Sb(IV) requires over 90 minutes. Furthermore, stability tests demonstrated that after 5 cycles of reaction, Ti/SnO2-Sb(II) showed no significant decrease in decolorization rate of MB, whereas Ti/SnO2-Sb(IV) exhibited a decline in decolorization performance towards MB starting from the 2nd cycle. This study revealed the crucial role of precursor salt boiling points in the formation of stable SnO2-based coated electrodes, providing a theoretical basis for the development of structurally stable and highly catalytic oxidation active coating electrodes.

Research on calcination thermal decomposition process of simulated high-level liquid waste based on two-step vitrification

The two-step vitrification process involves converting high-level waste from a liquid to a solid state through calcination, followed by melting the calcines with glass matrix material to form glassy wasteforms. The calcination process is a critical stage in the vitrification process. This study investigated the thermal decomposition performance and phase evolution of power reactor simulated high-level waste during the calcination process. As the calcination temperature increased from 100 to 900 °C, the resultant waste calcines showed increasingly darker color and smaller general particle sizes. Below 600 °C, the waste experienced thermal decomposition of nitrate and formate compounds, leading to an approximate 40 wt% weight reduction. At 600 °C, the waste's weight remained constant, and crystalline phases such as ZrxM1-xO2 (M = Ce, Pr, Nd), BaMoO4, CeO2, and GdxCe1-xO2 were observed.

Thermal structural damage and thermal decomposition characterization of GAP propellants with nitrate ester plasticizers

AbstractGAP and nitrate ester compounds are introduced into the solid propellant formulation as energetic binders and energetic plasticizing agents, respectively, to further enhance the energy level of solid propellants. However, under abnormal thermal conditions, various components within GAP propellants, especially nitrate ester plasticizers, can collectively result in the generation of a large number of voids within the propellant due to factors such as thermal stress and slow component decomposition. This phenomenon can impact the safety of solid rocket engines, necessitating research into their thermal decomposition processes and thermal damage structures. In this study, the thermal decomposition characteristics and gas products of GAP propellants with different nitrate ester plasticizer formulations were investigated using DSC‐TG and FT‐IR. The damage structure of GAP propellants heated under unignited conditions was studied through Micro‐CT, examining the influence of heating conditions and nitrate ester plasticizers on the thermal damage structure of GAP propellants. During heating, the thermal damage structure of GAP propellants was found to include voids generated within the GAP binder and cracks at the interface between the GAP binder and particles, with nitroglycerin as a plasticizer exacerbating the thermal damage of GAP propellants (about 2.2–2.9 times).

Method of neutralization of nitrogen oxides in area of low-temperature plasma

In the production of 1 ton of oxalic acid, 2000 m3 of gases with an average content of 2–2.5% of nitrogen oxides are emitted into the atmosphere. The existing methods of air purification from nitrous gases have a number of disadvantages and therefore cannot be widely used in industry. Based on theoretical and experimental studies, a new method for the thermal decomposition of nitrogen oxides has been developed, which provides for the sanitary purification of waste gases in the production of oxalic acid, up to the maximum permissible concentrations. The process of thermal decomposition of nitrogen oxides in the temperature range from 500 to approximately 50000С has been studied. To achieve such temperatures, an arc plasma torch with a tungsten cathode and a copper anode was used. The degree of decomposition was determined by measuring the NO concentration at the inlet and outlet by the evacuated flask method. The effects of gaseous (hydrogen, ammonia, methane, natural gas), liquid (kerosene, gasoline, fuel oil), and solid reducing agents (coke, coal, graphite) on the decomposition reaction of nitrogen oxides were also studied.

Design and evaluation of a kind of polymer-bonded explosives with improved mechanical sensitivity and thermal properties

The emergence of TKX-50, an energetic ionic salt with a high enthalpy of formation and low sensitivity, has opened a new path for the development of high-energetic, insensitive composite explosives. However, due to the poor interfacial binding properties of TKX-50 with conventional binders, there is a lack of effective guidance for the design of TKX-50 based composite explosives. To address the above issues, the interactions between carboxymethyl cellulose acetate butyrate (CMCAB) and other binders with explosives TKX-50/HMX were compared using the molecular dynamics method. Based on the simulations, TKX-50/HMX/CMCAB-based polymer-bonded explosives (PBXs) were prepared with CMCAB as binder, which displays a high binding energy (Ebind) with TKX-50 and high cohesive energy density (CED), and the effect of TKX-50 content on the performance of PBXs was investigated. The physical properties of PBXs, specifically the morphology, mechanical sensitivity, and thermal conductivity, were analyzed by SEM, sensitivity apparatus, and thermal conductivity meter, respectively. The specific heat capacity (Cp) and non-isothermal decomposition temperature of PBXs were tested by DSC, and then the corresponding thermal kinetic parameters were analyzed to evaluate their thermal safety. The adiabatic thermal decomposition processes of PBXs were tested using an ARC instrument. The decomposition mechanism and kinetics were also explored to further analyze their thermal stability and thermal safety under adiabatic conditions. The computer code EXPLO5 was used to predict the detonation parameters of PBXs. The results showed that CMCAB and TKX-50 displayed favorable interfacial bonding properties, and TKX-50 can be bonded with HMX to form a molding powder with a desirable morphology and safety profile. The TKX-50 in PBXs effectively improves the mechanical sensitivity and thermal safety of PBX and has a significant effect on the detonation performance of PBX. This research demonstrates a novel method suitable for screening and investigating high-energetic insensitive explosive systems compatible with TKX-50.

Highly-efficient flame-retarding unsaturated polyester resin via the designation of an expansive flame retardant

Unsaturated polyester resins (UPR) are commonly used in electronics manufacturing and traditional construction, but their inherent flammability greatly limits their use. An expansive flame retardant EZ was prepared via the simple ionic reaction between the 2-Aminothiazole (AMZ) and ethylene diamine tetra methylene phosphoric acid (EDTMP). The thermal decomposition process of EZ and UPR/EZ and the flame retardancy of the compound were studied. The flame retardancy mechanism of EZ in UPR was analyzed in detail. When the EZ content was 15 wt%, the flame-retardant grade of the composite reached V-0. The flame-retardant efficiency was very high mainly through the interaction of gas phase and condensed phase. Interestingly, flame retardant EZ can perform expansion crosslinking in UPR, which can effectively promote carbon formation in UPR. Moreover, EZ itself can also expand to form dense and continuous carbon layers in UPR, which further elucidates the flame-retardant mechanism.

Thermo-Structural Characterization of Phase Transitions in Amorphous Griseofulvin: From Sub-Tg Relaxation and Crystal Growth to High-Temperature Decomposition.

The processes of structural relaxation, crystal growth, and thermal decomposition were studied for amorphous griseofulvin (GSF) by means of thermo-analytical, microscopic, spectroscopic, and diffraction techniques. The activation energy of ~395 kJ·mol-1 can be attributed to the structural relaxation motions described in terms of the Tool-Narayanaswamy-Moynihan model. Whereas the bulk amorphous GSF is very stable, the presence of mechanical defects and micro-cracks results in partial crystallization initiated by the transition from the glassy to the under-cooled liquid state (at ~80 °C). A key aspect of this crystal growth mode is the presence of a sufficiently nucleated vicinity of the disrupted amorphous phase; the crystal growth itself is a rate-determining step. The main macroscopic (calorimetrically observed) crystallization process occurs in amorphous GSF at 115-135 °C. In both cases, the common polymorph I is dominantly formed. Whereas the macroscopic crystallization of coarse GSF powder exhibits similar activation energy (~235 kJ·mol-1) as that of microscopically observed growth in bulk material, the activation energy of the fine GSF powder macroscopic crystallization gradually changes (as temperature and/or heating rate increase) from the activation energy of microscopic surface growth (~105 kJ·mol-1) to that observed for the growth in bulk GSF. The macroscopic crystal growth kinetics can be accurately described in terms of the complex mechanism, utilizing two independent autocatalytic Šesták-Berggren processes. Thermal decomposition of GSF proceeds identically in N2 and in air atmospheres with the activation energy of ~105 kJ·mol-1. The coincidence of the GSF melting temperature and the onset of decomposition (both at 200 °C) indicates that evaporation may initiate or compete with the decomposition process.