Thermal stability of gelatin gels: Effect of preparation conditions on the activation energy barrier to melting

10, 20, and 40 wt.% aqueous gelatin gels were prepared under isothermal (annealing at 15, 20, and 25 °C for 15 to 120 min) and nonisothermal (cooling at 1 °C min⁻¹) conditions. Isoconversional kinetic analysis of DSC data on gel melting (gel-sol transition) of all types of gels revealed significant variations in the activation energy throughout the process. Activation energy barrier to melting of isothermally prepared gels was in the range 160-190 kJ mol⁻¹ and found to increase with increasing the annealing temperature that was the major effect discovered. Activation energy barrier to melting of nonisothermally prepared gels was determined to be around 120-140 kJ mol⁻¹ and increase with increasing the concentration. Local reversibility of the gel melting was demonstrated by using temperature modulated DSC.     

Crystallization and melting behaviors of poly(trimethylene terephthalate)

The crystallization and melting behaviors of poly(trimethylene terephthalate) (PTT) have been studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and solid-state NMR. At certain crystallization temperatures (T_c) for a given time, the isothermally crystallized PTT exhibits two melting endotherms, which is similar to that of PET and PBT. At higher crystallization temperature (T_c = 210 °C), the low-temperature endotherm is related to the melting of the original crystals, while the high-temperature endotherm is associated with the melting of crystals recrystallized during the heating. The peak temperatures of these double-melting endotherms depend on crystallization temperature, crystallization time, and cooling rate from the melt as well as the subsequent heating rate. At a low cooling rate (0.2 °C/min) or a high heating rate (40 °C/min), these two endotherms tend to coalesce into a single endotherm, which is considered as complete melting without reorganization. WAXD results confirm that only one crystal structure exists in the PTT sample regardless of the crystallization conditions even with the appearance of double melting endotherms. The results of NMR reveal that the annealing treatment increases proton spin lattice relaxation time in the rotation frame, T_1ρ ^H, of the PTT. This phenomenon suggests that the mobility of the PTT molecules decreases after the annealing process. The equilibrium melting temperature (T _m ^o ) determined by the Hoffman-Weeks plot is 248 °C.     

The crystallization morphology and melting behavior of polymer crystals in nano-sized domains

The crystallization morphology and the melting behavior of the phase-separating poly(?-caprolactone) (PCL) and poly(ethylene oxide) (PEO) blends were studied using atomic force microscopy. Two blends consisting of PCL and PEO with weight ratios of 10/90 and 90/10 were prepared to form the isolated spherical domains by the phase-separating process. The results show that the melting temperatures of the PCL and PEO lamellae in the confined domains increased as the lamellar length increased, and the melting behavior of the PCL and PEO lamellae in the matrix and confined domains was also studied.     

Isothermal and nonisothermal crystallization kinetics of bio-sourced nylon 69☆

Bio-sourced nylon 69,one of promising engineering plastics,has a great potential in developing sustainable technology and various commercial applications.Isothermal and nonisothermal crystallization kinetics of nylon 69 is a base to optimize the process conditions and establish the structure–property correlations for nylon 69,and it is also highly bene ficial for successful applications of nylon products in industry.Isothermal and nonisothermal crystallization kinetics has been investigated by differential scanning calorimetry for nylon 69,bio-sourced even–odd nylon.The isothermal crystallization kinetics has been analyzed by the Avrami equation,the calculated Avrami exponent at various crystallization temperatures falls into the range of 2.28 and 2.86.In addition,the Avrami equation modi fied by Jeziorny and the equation suggested by Mo have been adopted to study the nonisothermal crystallization.The activation energies for isothermal and nonisothermal crystallization have also been determined.The study demonstrates that the crystallization model of nylon 69 might be a twodimensional(circular)growth at both isothermal and nonisothermal crystallization conditions.Furthermore,the value of the crystallization rate parameter(K)decreases signi ficantly but the crystallization half-time(t1/2)increases with the increase of the isothermal crystallization temperature.To nonisothermal crystallization,the crystallization rate increases as the cooling rate increases according to the analysis of Jeziorny's theory.The results of Mo's theory suggest that a faster cooling rate is required to reach a higher relative degree of crystallinity in a unit of time,and crystallization rate decreases when the relative degree of crystallinity increases at nonisothermal crystallization conditions.     

Isothermal and nonisothermal crystallization kinetics of partially melting nylon 10 12

Nylon 10 12, a newly industrialized engineering plastic, shows a double‐melting phenomenon during melting. Partial melts were obtained when the sample was heated to the temperature between the two melting peaks. A differential scanning calorimeter was used to monitor the energies of the isothermal and nonisothermal crystallization from the partially melted samples. During isothermal crystallization, relative crystallinity develops with a time dependence described by the Avrami equation, with the exponent n = 1.0. For nonisothermal studies, kinetics treatments based on the Avrami and Ozawa equations are presented to describe the crystallization process. It was found that the two treatments can describe the nonisothermal crystallization from the partially melted samples. The derived Avrami and Ozawa exponents are all about 1.0, which means that the partially melted samples crystallize by one‐dimensional growth, which may cause thickening of the lamellae. We calculated the crystallization activation energies for isothermal and nonisothermal crystallization from the partially melted samples. It was found that the activation energy determined by the Kissinger method was not rational, which may be attributed to the free‐nucleation process for nonisothermal crystallization from partially melted samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1311–1319, 2003     

Effect of cooling rate and frequency on the calorimetric measurement of the glass transition

The glass transition of thermoplastics of different polydispersity and thermosets of different network structure has been studied by conventional differential scanning calorimetry (DSC) and temperature modulated DSC (TMDSC). The cooling rate dependence of the thermal glass transition temperature T_g measured by DSC, and the frequency dependence of the dynamic glass transition temperature T measured by TMDSC have been investigated. The relation between the cooling rate and the frequency necessary to achieve the same glass transition temperature has been quantified in terms of a logarithmic difference Δ=log₁₀[|q|]−log₁₀(ω), where |q| is the absolute value of the cooling rate in K s⁻¹ and ω is the angular frequency in rad s⁻¹ necessary to obtain T_g(q)=T(ω). The values of Δ obtained for various polymers at a modulation period of 120 s (frequency of 8.3 mHz) are between 0.14 and 0.81. These values agree reasonably well with the theoretical prediction [Hutchinson JM, Montserrat S. Thermochim Acta 2001;377:63 [6]] based on the model of Tool–Narayanaswamy–Moynihan with a distribution of relaxation times. The results are discussed and compared with those obtained by other authors in polymeric and other glass-forming systems.     

Influence of chain length in nonyl-phenol ethoxylate surfactants on the film formation behaviour of methylmethacrylate-2-ethylhexyl acrylate copolymer latexes: part 1. Differential scanning calorimetry and atomic force microscopy

A comparison of the film forming characteristics of methylmethacrylate-2-ethylhexyl acrylate latex copolymers stabilised with nonyl-phenol ethoxylate molecules of varying chain lengths is presented. The ability of the stabiliser to segregate and diffuse from the interfacial layer into the surrounding media influences both the rate of coalescence process and structure of the film formed. Dynamic mechanical analysis, minimum film formation temperature measurements, particle size analysis, differential scanning calorimetry (DSC) and atomic force microscopy reveal the complexity of the mechanism involved in the coalescence process. A model that describes the various stages of coalescence and compaction of the latex particles indicates the effects of chain length on the film forming properties. For the stabiliser with a chain length of 20, coalescence is observed at room temperature; whereas for the stabiliser with chain lengths of 30 and 40, coalescence only occurs if the films are raised above 315 K. For the longer chain stabilisers, the effect of stabiliser-stabiliser interaction inhibits the coalescence process and DSC data indicate the occurrence of crystalline phase structure in the thin film.     

A nucleation mechanism leading to stacking of lamellar crystals in polymer thin films

Systematic studies based on well‐controllable model systems aim at understanding how crystallization from a melt or solution of randomly coiled polymers leads to the formation of mono‐lamellar crystals. However, besides mono‐lamellar crystals also various other morphologically simple but yet not well understood structures are found. In particular, stacks of correlated lamellar crystals have been observed since the early days of the study of polymer crystallization. Here, we demonstrate that a recently proposed mechanism of self‐induced nucleation within lamellar crystals provides a possibility to explain how in such stacks lamellar crystals can be correlated. Examining various polymer systems, we show that the probability for generating self‐induced nuclei depends on the morphology of an initiating dendritic basal lamellar crystal. In addition, we provide evidence that this self‐induced nucleation mechanism, together with a high rate of transport of molten polymer to the fold surface, may allow the formation of polymer crystals with similar size in all three dimensions, containing a large number of superposed correlated lamellae. © 2019 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Effect of nucleation mechanism on complex poly(L‐lactide) nonisothermal crystallization process,part 2: Crystallization kinetics analysis

In the first part of this article, we reported the crystalline memory effect on the nonisothermal crystallization of poly(L ‐lactide). The experiments were carried out by using polymer single crystals growth from dilute solution as standard starting material. In this article (Part II), we have analyzed in detail the effect of the melting condition on the overall crystallization kinetics by applying the Nakamura‐Avrami model to DSC results. The absence or the low concentration of foreign infusible heterogeneous nuclei in our system allowed us to exalt the self‐nuclei role in polymer crystallization, to follow their concentration decrease during the melting process and to find the limiting melting temperature for their disappearance. Below such a temperature, a stable equilibrium number of self‐nuclei was observed, probably deriving from ordered structures, persisting in the melt, and originated from the single crystals thickening process during the polymer dynamic melting in the DSC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution

Carbonation decomposition of hydrogarnet is a significant reaction of the calcification-carbonation new method for alumina production by using low-grade bauxite. In this work, non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution was studied by high-pressure differential scanning calorimetry (HPDSC) at different heating rates of 2, 5, 8, 10, 15 and 20 K·min^-1, respectively. The activation energy (E_a) was calculated with the help of isoconversional method (model-free), and the reaction mechanism was determined by the differential equation method. The calculated activation energy of this reaction was 115.66 kJ·mol^-1. Furthermore, the mechanism for decomposition reaction is Avrami-Erofeev (n = 1.5), and the decomposition process is diffusion-controlled.     

Nonisothermal curing kinetics of a novel polymer containing phenylsilylene and propargyl–hexafluorobisphenol a units

A novel thermosetting polymer, poly[(phenylsilylene) propargyl–hexafluorobisphenol A] (PBAFS), with a new structure was synthesized. The structure of PBAFS and its cured resins were characterized by Fourier transform infrared spectra. During curing, a hydrosilylation reaction may occur between Si? H and C?C bonds and a Claisen rearrangement reaction of aryl propargyl ether led to formation of chromene, which immediately preceded polymerization on heating. The dynamic viscosity behavior was investigated by rheological experiment. Thermal stability of the cured PBAFS was also measured by Thermogravimetric analysis. The curing behavior of PBAFS was monitored by nonisothermal differential scanning calorimetry at different heating rates. The kinetic parameters and the kinetic model of the cure reaction were evaluated by Kissinger, Ozawa, and Friedman methods. The cure reaction of PBAFS was found nth‐order in nature and the prediction curves by Friedman method for nonisothermal curing reaction were in good agreement with the experimental curves. The isothermal curing time of PBAFS were predicted by Vyazovkin and model‐fitting methods from the nonisothermal kinetic parameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The use of differential scanning calorimetry to study polymer crystallization kinetics

A Tektronix-31 programmable calculator interfaced to a Perkin Elmer differential scanning calorimeter, model 2, substantially improves the accuracy of measuring the time-dependent development of the degree of crystallinity (× 10) and hence improves the quality of the rate data. Storing energy flow data at preset time intervals directly into the memory of the calculator improves the accuracy of the measurement of time, and enables the evaluation of the onset of crystallization and the baseline of the calorimeter initially. This substantially improves the measurement of the degree of crystallinity developing with time by integrating the energy flow data over the time interval from the onset of crystallization. Polyethylene samples are studied since their rate constants have a marked temperature dependence which enables the accuracy of the analytical procedure to be assessed. Primary and secondary crystallization processes are separated.     

Analytical expressions for transient melting of polymer pellet sliding against adiabatic wall

The melting of polymer caused by friction before the solid plug is formed is an important phenomenon in the plastic injection process. To analyze the melting process caused by solid particles sliding against the bellow, a method that can simulate behavior of each particle during the calculation should be used. Particle element numerical method is hence adopted in the analysis for this research to take into consideration the behavior of each particle, where the melting of pellets caused by friction against flight and screw are assumed as friction against adiabatic walls. In this paper, analytical expressions of the transient melting process for spherical polymer pellets sliding against adiabatic wall are derived, which is essential for the numerical simulation of melting process in solid conveying section by particle element method.     

Solid Fat Content Estimation by Differential Scanning Calorimetry: Prior Treatment and Proposed Correction

The objective of this work was to develop a corrected method for solid fat content estimation by differential scanning calorimetry (DSC), as important differences are usually observed between the results given by DSC and pulsed nuclear magnetic resonance (NMR). Cold storage after full melting of fats was necessary to avoid the appearance of exothermic peaks in the modulated temperature DSC thermograms, in order to make an appropriate estimation of melting energy. Different fats were analyzed by NMR and DSC, obtaining considerably higher solid fat content values with the latter, uncorrected method. These differences were attributed to the fact that consumed energy per unit of melted mass tends to increase with the increase of the melting temperature of each fraction of the fats. A linear correlation between melting enthalpy and melting point of different triglycerides was used to estimate the energy per unit of mass consumed at each temperature. From these data, an estimated transformation of melting energy into melted mass was performed and new solid fat content values were calculated. The results obtained from this correction were much closer to the measurements made by NMR, in comparison to the uncorrected DSC method.     

Crystallization kinetics and melting behavior of nylon 10,10 in nylon 10,10–montmorillonite nanocomposites

The crystallization kinetics and melting behavior of nylon 10,10 in neat nylon 10,10 and in nylon 10,10–montmorillonite (MMT) nanocomposites were systematically investigated by differential scanning calorimetry. The crystallization kinetics results show that the addition of MMT facilitated the crystallization of nylon 10,10 as a heterophase nucleating agent; however, when the content of MMT was high, the physical hindrance of MMT layers to the motion of nylon 10,10 chains retarded the crystallization of nylon 10,10, which was also confirmed by polarized optical microscopy. However, both nylon 10,10 and nylon 10,10–MMT nanocomposites exhibited multiple melting behavior under isothermal and nonisothermal crystallization conditions. The temperature of the lower melting peak (peak I) was independent of MMT content and almost remained constant; however, the temperature of the highest melting peak (peak II) decreased with increasing MMT content due to the physical hindrance of MMT layers to the motion of nylon 10,10 chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2181–2188, 2003     

Synthesis and characterization of a new hyperbranched organic–inorganic solid polymer electrolyte with cyanuric chloride as a core element

A new hyperbranched organic–inorganic hybrid electrolyte based on the use of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, CC) as the coupling core to couple with oligo(oxyalkylene)-amines, followed by condensation with (3-glycidoxypropyl)-trimethoxysilane (GLYMO) and complexed with LiClO₄, has been prepared and characterized. The Vogel–Tamman–Fulcher (VTF) like conductivity behavior is observed in the present organic–inorganic hybrid electrolytes with a maximum ionic conductivity value of 4.4 × 10⁻⁵ S cm⁻¹ at 30 °C. Multinuclear NMR techniques are used to provide a microscopic view for the specific interaction between the polymer chains and Li⁺ cations and their dynamic behaviors. The results of 2D ¹H–¹³C wide-line separation (WISE) and ⁷Li static line NMR width measurements divulge that the mobility of the ⁷Li cations is strongly related to a dynamic environment created by the polymer motion in the amorphous phase. The combined results of conductivity and ⁷Li pulse-gradient spin-echo (PGSE) NMR self-diffusion coefficient measurements reveal that the conductivity enhancement at low salt concentrations is mainly caused by the high mobility of the lithium cations.     

The kinetic study of the curing reaction of mono- and di-epoxides obtained during the reaction of divinylbenzene and hydrogen peroxide with acid anhydrides

In this paper, the non-isothermal differential scanning calorimetry (DSC) was employed to investigate the cure process and to determine the kinetic parameters of the curing reactions of mono- and di-epoxides with maleic and glutaric anhydrides. The epoxides were obtained during the epoxidation process of commercially available divinylbenzene by using 60% hydrogen peroxide as the oxidant in the presence of organic solvents and magnesium oxide as the catalyst. It was found that the cure process of epoxides with maleic anhydride was described through higher values of enthalpy of polymerization (ΔH_R) and lower temperatures of the cure initiation (T_onset), the peak maximum temperature (T_max) and the final cure temperature (T_end). It can be considered to accelerate the rate of reaction and lead to an excellent network structure when maleic anhydride was used as curing agent. The kinetic analysis was firstly computed using a model free-estimation of the activation energy (Friedman, Ozawa-Flynn-Wall methods) and then the multivariate non-linear regression with a 6th degree Runge-Kutta process in a modified Marquardt procedure was employed to calculate the corresponding kinetic parameters (E_i, n_i, A_i) using the nth-order reaction f(α). The unbranched three-step process of the nth-order reaction f(α) for each step was the best to describe the cure process of mono- and di-epoxide with acid anhydrides. The determined values of the activation energies were in the range 64.7-105.2 kJ/mol for epoxides/glutaric anhydride system and 64.7-82.7 kJ/mol when maleic anhydride was used as hardening agent.