Investigation of alkaline hydrolysis of polyethylene terephthalate by differential scanning calorimetry and thermogravimetric analysis

The hydrolytic depolymerization of polyethylene terephthalate (PET) with alkaline hydroxides was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The reactions of the mixtures were conducted in their solid states under nitrogen atmosphere. The experimental results showed that potassium hydroxide possessed the hydrolytic activity of depolymerizing PET into small molecules such as ethylene glycol; in contrast, sodium hydroxide did not. The production rate of ethylene glycol was enhanced by increasing charge ratio of potassium hydroxide to PET. The presence of water facilitated the alkaline hydrolysis of PET; however, the presence of metal acetates decreased the hydrolysis rate. The activation energy for alkaline hydrolysis of PET determined by the thermograms was in good agreement with the value obtained from the experiments in a batch reactor. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1939–1945, 1998     

Thermal analysis of failed-batch palm oil by differential scanning calorimetry

Thermal behavior of palm oil samples drawn from the batch crystallizers that failed during crystallization and of a control oil that was drawn from a batch that produced good crystallization were analyzed by differential scanning calorimetry under constant heating and cooling conditions. Four polymorphs—β’₂, α, β’₁, and β₁—were observed, and their temperatures were tabulated. A rapid and sudden surge of heat demand was observed for samples from failed crystallizers. Less supercooling values were obtained from the control oil compared to the higher values for samples from failed crystallizers. In crystallization thermograms, a sharp high-temperature exotherm (high-T peak) and a broad low-temperature exotherm (low-T peak) were observed. Low-T peaks were found almost invariably stationary at −5.1 to −5.6°C, and high-T peaks varied depending on the saturation level of the oil. A new peak, sandwiched between the high-T and low-T peaks, was observed for the control oil.     

Characterization of petroleum bitumens and their fractions by thermogravimetric analysis and differential scanning calorimetry

Thermogravimetric analysis (t.g.a.) and differential scanning calorimetry (d.s.c.) were applied to the characterization of petroleum bitumens and their chromatographic fractions. The influence of the different constituents on the thermal stability of bitumens was studied by t.g.a. Characteristics such as the glass transition temperature (T_g) and the percentage crystallized fraction of these samples were determined by d.s.c. The information obtained from thermal analysis is shown to be suitable for correlation with the composition and the physical properties of these products. Hence the characterization of the thermal behaviour of bitumens and related compounds may provide a useful initial step for further studies on their chemical and physical features.     

Activation energy and curing behavior of resol‐ and novolac‐type phenolic resins by differential scanning calorimetry and thermogravimetric analysis

The thermal behavior, thermal degradation kinetics, and pyrolysis of resol and novolac phenolic resins with different curing conditions, as a function of the formaldehyde/phenol (F/P) molar ratio (1.3, 1.9, and 2.5 for the resol resins and 0.5, 0.7, and 0.9 for the novolac resins) were investigated. The activation energy of the thermal reaction was studied with differential scanning calorimetry at five different heating rates (2, 5, 10, 20, and 40°C/min) between 50 and 300°C. The activation energy of the thermal decomposition was investigated with thermogravimetric analysis at five different heating rates (2, 5, 10, 20, and 40°C/min) from 30 to 800°C. The low molar ratio resins exhibited a higher activation energy than the high molar ratio resins in the curing process. This meant that less heat was needed to cure the high molar ratio resins. Therefore, the higher the molar ratio was, the lower the activation energy was of the reaction. As the thermal decomposition of the resol resins proceeded, the activation energy sharply decreased at first and then remained almost constant. The activation energy of the thermal decomposition for novolac resins with F/P = 0.5 or F/P = 0.7 was almost identical in all regions, whereas that for novolac resins with F/P = 0.9 gradually decreased as the reaction proceeded. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2589–2596, 2003     

Measurement of bound water content in sludge: The use of differential scanning calorimetry (DSC)

The bound water content of original and frozen activated sludge and an inorganic sludge were measured via differential scanning calorimetry (DSC) and drying tests. Original sludge contained a significant level of bound water which was reduced by about 50% after freeze/thaw treatment. A simple thermodynamic interpretation showed that liquid–solid binding strength played an important role in depression of the freezing point of bound water in a sludge. The choice of a threshold temperature in a DSC test was equivalent to definition of a threshold binding strength dividing bound/non-bound water content. The possible close relationship between the bound water content measured via DSC and the drying test is discussed. The importance for sample uniformity was also examined.     

Poly(lactic acid)/polystyrene bioblends characterized by thermogravimetric analysis,differential scanning calorimetry,and photoacoustic infrared spectroscopy

Bioblends are composites of at least one biodegradable polymer with nonbiodegradable polymer. Successful development of bioblends requires that the biodegradable polymers be compatible with other component polymers. Compatibility can be assessed by evaluating the intermolecular interactions between the component polymers. In this work, the interaction in binary bioblends comprising biodegradable poly(lactic acid) (PLA) and polystyrene (PS) was investigated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and Fourier transform infrared photoacoustic spectroscopy (FTIR‐PAS). The TGA studies indicated that incorporation of PLA in PS resulted in thermal destabilization of PS. The DSC studies showed that some parameters favored partial miscibility of PS in PLA, while others favored immiscibility, such as the existence of two glass transitions. The FTIR‐PAS spectra revealed the presence of intermolecular n–π interactions between PLA and PS and indicated that the degree of interaction was dependent on the concentrations of the polymers in the bioblends. FTIR‐PAS results computed via differential spectral deconvolution were consistent with, and therefore support, the results of TGA and DSC analyses of PLA/PS bioblends. The degradation kinetics, used to determine the degradation mechanism, revealed a two‐ or three‐step mechanism. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Analysis of the chemical composition distribution of ethylene/α-olefin copolymers by solution differential scanning calorimetry: an alternative technique to Crystaf

A series of ethylene/1-hexene copolymers synthesized with a metallocene catalyst with varying comonomer contents but constant molecular weights were analyzed with crystallization analysis fractionation (Crystaf), solid state differential scanning calorimetry (solid state DSC) and solution differential scanning calorimetry (solution DSC). Experimental solution DSC exotherms were compared to Crystaf profiles obtained under similar crystallization conditions. At the same cooling rates (0.1 °C/min), considerable differences were found for samples with low levels of short chain branching although the discrepancy became less significant with increasing branching. Very good agreement was found between the Crystaf profiles of metallocene copolymers obtained at a cooling rate of 0.1 °C/min and solution DSC exotherms of samples crystallized at the rate of 0.01 °C/min. Good agreement was also observed between the Crystaf and solution DSC profiles of a Ziegler-Natta linear low-density polyethylene (LLDPE) sample when crystallized at the same cooling rate of 0.2 °C/min. In conclusion, solution DSC is a useful technique for simulating profiles obtained by Crystaf analysis, although very slow analysis times must be used for samples with less than 4 mol% comonomer.     

Miscibility characterization of SMA/SAN and SMA/PMMA blends by differential scanning calorimetry and fluorescence techniques

In this study, styrene‐maleic anhydride (SMA) copolymer was modified by monoesterification method with 9‐(hydroxymethyl)anthracene fluorophore to prepare a fluorescent anthracene labeled SMA (SMA‐An) material. The latter was then characterized by attenuated total reflection (ATR) and thermogravimetric analysis (TGA) techniques. In the second step of this work, SMA‐An was added to SMA/[Styrene‐Acrylonitrile Copolymer (SAN)] and SMA/[Poly(methyl methacrylate) (PMMA)] blends to investigate the miscibility of these blends at the molecular level. The miscibility of SMA/PMMA blends was characterized using fluorescence quenching of anthracene by the succinic anhydride and succinic acid functions on SMA macromolecule itself. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Kinetics of commercial olive oil oxidation: Dynamic differential scanning calorimetry and Rancimat studies

Four samples of olive oil were oxidized under polythermal (dynamic) conditions in the cell of a normal‐pressure differential scanning calorimeter (DSC) and in the Metrohm Rancimat apparatus. The DSC experiments were carried out in an oxygen flow atmosphere using different linearly programmed heating rates in the range of 4–20 °C/min. Through DSC exotherms, the extrapolated onset temperatures were determined and used for the assessment of the thermal‐oxidative stabilities of the samples. Using the Ozawa‐Flynn‐Wall method and the Arrhenius equation, the activation energies (E_a), pre‐exponential factors (Z) and reaction rate constants (k) for oil oxidation under DSC conditions were calculated. The Rancimat measurements of oxidation induction times were carried out under isothermal conditions in an air atmosphere at temperatures from 100 to 140 °C with intervals of 10 °C. Using the Arrhenius‐type correlation between the inverse of the induction times and the absolute temperature of the measurements, E_a, Z, and k for oil oxidation under Rancimat conditions were calculated. The primary kinetic parameters derived from both methods were qualitatively consistent and they help to evaluate the oxidative stabilities of oils at increased temperatures.     

Determination of the crystalline phases of poly(vinylidene fluoride) under different preparation conditions using differential scanning calorimetry and infrared spectroscopy

A method with good precision has been developed to quantitatively measure the degree of α‐, β‐, and γ crystallinity in poly(vinylidene fluoride) (PVDF) by means of infrared spectroscopy. The phase composition of solution‐deposited PVDF films was found to be strongly influenced by the presence of hydrophilic residues on the silicon substrate, the relative humidity present at film deposition, the spatial position on the substrate, and the thermal treatment of the deposited film. Films produced on pristine surfaces gave predominantly α‐phase PVDF, but when a layer of polar solvent (acetone or methanol) remained on the surface, the films produced were predominantly γ phase. Higher humidity promoted a higher fraction of γ crystallinity in the solution‐deposited PVDF films. Solution‐cast films had highly variable composition across the substrate, whereas spin‐cast films were uniform. High‐temperature annealing of PVDF films normally converts the polymer to the γ phase, but annealing the film while still attached to the silicon substrate inhibited this phase transformation. Low‐temperature annealing of freestanding films led to a previously unreported thermal event in the DSC, a premelting process that is a kinetic event, assigned to a crystalline relaxation. Higher‐temperature annealing gave a double endotherm, assigned to melting of different‐sized crystalline domains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1093–1100, 2003     

Differential scanning calorimetry analysis of the thermal treatment of ternary mixtures of ethylene vinyl acetate,polyethylene, and azodicarbonamide

The different transitions and reactions involved in the thermal processing of ternary ethylene vinyl acetate (EVA)–polyethylene (PE)–azodicarbonamide (ADC) mixtures with different concentrations of PE and ADC, which was used as a foaming agent, were studied by means of differential scanning calorimetry. The effect of the concentration of PE in the ternary samples was practically linear, which showed an increase in the fusion heat of the PE and the PE domains of the EVA. On the contrary, the mechanism of the thermal decomposition of ADC that the ternary mixtures contained was strongly dependent on its concentration in the sample, which showed clear deviations from linearity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improvement of the thermal stability of polyhydroxybutyrates by grafting with maleic anhydride by different methods: Differential scanning calorimetry,thermogravimetric analysis,and gel permeation chromatography

The crystallization and thermal degradation behaviors of polyhydroxybutyrate (PHB) grafted with maleic anhydride (MA) by different techniques were analyzed with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). The results of DSC, TGA, and GPC analyses indicated that the grafting method could affect the crystallization rate, crystallinity, and thermal stability of PHB because of changes in the molecular weight of PHB and the amount of MA grafted during the reaction. The reduction of the molecular weight of PHB that reacted during the processing followed this order of methods: melt grafting > solvent grafting > mechanical grafting. However, the grafting ratio of MA followed this order of methods: melt grafting > mechanical grafting > solvent grafting. All three grafting methods significantly improved the thermal stability, therefore increasing the crystallization rate and melting temperature of the as‐received PHB. A grafting ratio of MA as low as 0.07 wt % could result in a significant improvement in the heat resistance of PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Probing the interface behaviour of injection molded thermoplastics by micro-thermal analysis and temperature-modulated differential scanning calorimetry

Micro-thermal analysis (μTA™) and temperature-modulated differential scanning calorimetry (TMDSC) are emerging as powerful instruments for identifying the existence and quantities of phases in multi-component systems, as well as interfacial properties. In this study, these two complimentary techniques are utilised to probe the interphase behaviour of a polycarbonate/acrylonitrile-styrene-acrylate (PC/ASA) blend as they develop during injection molding. Micro-thermal analysis revealed that parts manufactured at high injection time, pack pressure and melt temperature show a densely packed bulk morphology, a significant amount of particle agglomeration as well as the formation of styrene-acrylonitrile/PC (SAN/PC) interphases. TMDSC qualitatively and quantitatively characterized the PC/ASA's multi-phase morphology and its interfacial properties both before and after injection molding, indicating a greater amount of PC entering the interphase than SAN.     

Glass transition temperatures of hydrocarbon blends: Adhesives measured by differential scanning calorimetry and dynamic mechanical analysis

A comparison of calculated and measured glass transition temperatures of a series of three‐component hydrocarbon blends was performed. The blends were prepared as mixtures of an elastomer with different proportions of tackifying resin and oil. Glass transition temperature, T_g, was measured by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) at four measurement frequencies. Most of these blends had pressure‐sensitive adhesive (PSA) properties, and were used to prepare a series of PSA tapes. The adhesion of the PSA tapes was shown to be strongly dependent on T_g. Tack of PSA tapes was measured at two different temperatures, and shown to be directly correlated to the blend T_g. Several predictive methods for blend T_g that are based on individual component T_gs were evaluated. The prediction of blend T_g is far more accurate if the individual component T_g values are determined by DMA instead of DSC. In addition, the Gordon‐Taylor equation gave a significant improvement on predicted blend T_g when compared to the Fox equation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 826–832, 2000     

Use of rheology, dielectric analysis and differential scanning calorimetry for gel time determination of a thermoset

Measurements of gel time of the epoxy system DGEBA(n=0)/m-XDA were carried out using rheometry and dielectric analysis with the objective of checking the validity of Mangion-Johari equation (DEA) and Harran-Laudouard criterium (rheometry) for gel time determination. In this work, gel times obtained by rheometry and dielectric analysis are compared and conversions at gel time calculated. From the experimental results obtained for gel times it was found a reasonable agreement between the two techniques that lead to gel conversion values very close to those obtained using Flory equation.     

Thermal decomposition of potassium permanganate: Thermogravimetry,differential scanning calorimetry and hot-stage microscopy studies

Thermogravimetry (TG), differential scanning calorimetry (d.s.c.), and hot-stage microscopy (HSM) techniques have been applied in a study of the thermal decomposition of potassium permanganate. Single crystals of potassium permanganate and ground samples are studied at heating rates from 0.62 to 10 °C min^?1, and results compared with previous isothermal studies. Comparison of theoretical and experimental weight loss is made, for both forms of potassium permangante, and a possible mechanism based on diffusion chain theory and nucleation suggested.     

Expandable styrene/methyl methacrylate copolymer: Synthesis and determination of VOCs by combined thermogravimetry/differential thermal analysis‐gas chromatography/mass spectrometry

Parts cast of metals using expandable polystyrene foams may have an unacceptable amount of surface defects, such as lustrous carbon. The use of foams made of styrenic/acrylic copolymers can improve the quality of foam molds and metal parts made using such molds. Lost foam copolymer was synthesized by suspension copolymerization of styrene and methyl methacrylate. The polymerization was carried out in the presence of blowing agents. The decomposition products of lost foam beads were studied by a method composed of the thermogravimetry/differential thermal analysis (TG/DTA) and gas chromatography/mass spectrometry (GC/MS). With these systems, the TG/DTA data can be combined with a GC separation and MS identification methods. This combined method improves the analysis of the decomposition products of lost foam beads and enables the precise identification of the amount and the nature of volatile organic compounds (VOCs) trapped during suspension polymerization. The results obtained from the combined method were verified for the nature and amount of VOCs with the results of time‐conversion studies for copolymerization of monomers in the presence of different concentrations of blowing agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determination of dielectric and calorimetric properties in the cure reaction of two thermosets by dielectric analysis and differential scanning calorimetry

Dielectric analysis and differential scanning calorimetry were used to study the cure reaction of an epoxy resin (the diglycidyl ether of bisphenol A (DGEBA) (n = 0)) and two curing agents, ie 1,2‐diamine cyclohexane (1,2‐DCH) and m‐xylylenediamine (m‐XDA). Various dielectric properties, such as the relaxed permittivity, unrelaxed permittivity and dipole strength, were determined as a function of the curing time, temperature and conversion. The dielectric curing properties observed were related to geometric and energetic aspects of the samples. Analysis of the results shows that the relaxed permittivity and dipole strength are higher for the system DGEBA (n = 0)/1,2‐DCH than for the system DGEBA (n = 0)/m‐XDA. Copyright © 2005 Society of Chemical Industry     

Insight into thermal,crystallization kinetics,and phase behaviors of palm kernel oil and its olein/stearin by differential scanning calorimetry

The fractionation of oils has received considerable research attention, aiming at the modification of the properties of oils. The thermal and crystallization properties of palm kernel oil (PKO) and its olein/stearin (PKOL/PKST) were systematically investigated using differential scanning calorimetry (DSC). Based on the isothermal DSC results, crystallization temperature exerted critical effect on co-crystallization of PKOL and PKST. Moreover, it is reported that PKOL could be further separated by controlling the crystallization temperature, while PKST is hard to be further separated. The PKOL/PKST mixtures with different compositions were prepared and subjected to dynamic DSC analysis. The results illustrated that PKO meets the phase equilibrium of quasi-solid solutions.