Reversible and irreversible heat capacity of poly[carbonyl(ethylene‐co‐propylene)] by temperature‐modulated calorimetry

The heat capacity of poly[carbonyl(ethylene‐co‐propylene)] with 95 mol % C₂H₄? CO? (Carilon EP®) was measured with standard differential scanning calorimetry (DSC) and temperature‐modulated DSC (TMDSC). The integral functions of enthalpy, entropy, and free enthalpy were derived. With quasi‐isothermal TMDSC, the apparent reversing heat capacity was determined from 220 to 570 K, including the glass‐ and melting‐transition regions. The vibrational heat capacity of the solid and the heat capacity of the liquid served as baselines for the quantitative analysis. A small amount of apparent reversing latent heat was found in the melting range, just as for other polymers similarly analyzed. With an analysis of the heat‐flow rates in the time domain, information was collected about latent heat contributions due to annealing, melting, and crystallization. The latent heat decreased with time to an even smaller but truly reversible latent heat contribution. The main melting was fully irreversible. All contributions are discussed in the framework of a suggested scheme of six physical contributions to the apparent heat capacity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1565–1577, 2001     

Reversed Annealing of Thermal Fractionated Polyethylenes by TMDSC

Polyethylene samples prepared by thermal fractionation (TF) were annealed in several consecutive cycles in a temperature modulated DSC (TMDSC) at a temperatures one °C below the peak temperatures, increased from cycle to cycle relative to these peaks. The transition enthalpy of each cooling cycle was greater or equal to that of the preceding heating cycle. The total heat-flows of each heating cycle corresponded to those of the samples in the reference state up until the vicinity of the annealing temperature. During the annealing, the heat capacities decreased to a lower value over a one minute period. The thermal memory effect caused by the thermal fractionation was eliminated by a small overheating of the material for a short time. The fast disappearance of the thermal memory by a relatively very small degree of heating above their melting temperature denies a long range physical separation of macromolecules by TF. This revised version was published online in July 2006 with corrections to the Cover Date.     

步进扫描差示扫描量热法研究不同链结构的聚乙烯类聚烯烃热力学特性

采用步进扫描差示扫描量热法研究了几种具有不同链结构的聚乙烯类聚烯烃的热力学性质.结果表明,不同链结构的聚烯烃在热力学平衡熔融态下,其绝对比热容的温度依赖性在实验误差范围内几乎相同;而无论链结构的变化如何,在极低温度下稳定结晶态的热容也非常接近.但在熔融温度范围内,比热容对不同聚烯烃的链结构非常敏感,这是由于在远低于聚烯烃主熔化峰温度范围内,聚乙烯晶体结构中的不同支链的影响.在时间-热流的步进扫描曲线中,具有长支链结构的聚烯烃表现出独特的熔融-再结晶行为,这可能是由于交联点之间较长的受约束链段的运动在熔融过程中得到释放并重排所致.     

A Detailed Comparison of First Order Transitions by DSC and TMC

Indium was analyzed with both, standard differential scanning calorimetry (DSC) and temperature-modulated DSC (TMDSC) using sinusoidal and saw-tooth modulation. Instrument and sample effects were separated during nucleated, reversible melting and crystallization transitions, and irreversible crystallization with supercooling. The changes in heat flow, time, and sample and reference temperatures were correlated as functions of heating rate, mass, and modulation parameters. The transitions involve three regions of steady state (an initial and a final region before and after melting/crystallization, a region while melting/crystallization is in progress) and one region of approach to steady state (melting peak to final steady state region). Analyses in the time domain show promise when instrument lags, known from DSC, are used for correction of TMDSC. A new method of integral analysis is introduced for quantitative analysis even when irreversible processes occur in addition to reversible transitions. The information was derived from heat-flux calorimeters with control at the heater block or at the reference temperature sensor. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural Studies on PEK/TPI Blends

Blends of poly(ether ketone) (PEK) with poly(terephthaloyl-imide) (a thermoplasticpolyimide, TPI) were studied by temperature-modulated DSC (TMDSC) and X-ray diffraction. Samples were prepared by compression moulding of the premixed materials at 400°C and quenched to prevent crystallisation.The amorphous blends showed a single glass transition but with a jump in the temperature value at 60 mass% of PEK, indicating limited miscibility of the system at both sides of the composition series in the quenched, glassy state. Two cold crystallisation peaks over the concentration range 30 to 70 mass% of PEK were observed, but only one for all other compositions. A single melting peak was observed in all systems.Blends crystallised from the glassy state showed eutectic behaviour with the presence of the crystals of both pure components. This is the first reported case of two semicrystalline polymers exhibiting eutectic co-crystallisation. The formation of eutectic crystals is proof of full miscibility of the two polymers in their liquid state, i.e. at a temperature of 400°C and above. Blends cooled from the melt at a cooling rate of 2 K min^–1 showed a single glass transition and an extended melting range.Crystallisation during a second melting run generally starts at a different temperature then during the first run indicating chemical changes occurred in the molten state. This change was also verified by an exothermic peak above the melting temperature using TMDSC.This revised version was published online in November 2005 with corrections to the Cover Date.     

Study on thermal properties of organic ester phase-change material embedded with silver nanoparticles

This study investigates the thermal properties of new silver nano-based organic ester (SNOE) phase-change material (PCM) in terms of latent heat capacity, thermal conductivity and heat storage and release capabilities experimentally. Spherical-shaped surface-functionalized crystalline silver nanoparticles (AgNP) prepared were embedded in mass proportions of 0.1 through 5.0 wt% into the pure (base) PCM. Experimental results reveal that dispersion of AgNP into PCM was effective, only physical and no chemical interaction between AgNP and PCM has been exhibited; thereby phase-change temperature of SNOE PCMs were acceptable. These are essential characteristics for SNOE PCMs which signified their thermal and chemical stability on long term. Test results suggest that while compared to pure PCM, degree of supercooling was reduced by 11.7–6.8 % for aforesaid mass proportions of AgNP, whereas latent heat capacities decreased by 7.88 % in freezing and 8.91 % in melting. The interdependencies between thermophysical properties in improving nucleation and growth rate of stable SNOE PCM crystals were signified and discussed. Thermal conductivity of SNOE PCMs were enhanced from 0.284 to 0.765 W m^?1 K^?1 which was expected to be a 10–67 % increase for the above mass loading of AgNP. Furthermore, for SNOE PCMs enhancement span in freezing and melting cycles was improved by 41 and 45.6 %, respectively. Similarly, cooling and melting times were reduced by 30.8 and 11.3 %, respectively. Embedded AgNP helps to achieve improved thermophysical and heat storage characteristics for SNOE PCMs, which in turn can be considered as a potential candidate for cool thermal energy storage applications.     

Thermal memory of poly(3‐hydroxybutyrate) using temperature‐modulated differential scanning calorimetry

The influence of thermal history on morphology, melting, and crystallization behavior of bacterial poly(3‐hydroxybutyrate) (PHB) has been investigated using temperature‐modulated DSC (TMDSC), wide‐angle X‐ray diffraction (WAXRD) and polarized optical microscopy (POM). Various thermal histories were imparted by crystallization with continuous and different modulated cooling programs that involved isoscan and cool–heat segments. The subsequent melting behavior revealed that PHB experienced secondary crystallization during heating and the extent of secondary crystallization varied with the cooling treatment. PHB crystallized under slow, continuous, and moderate cooling rates were found to exhibit double melting behavior due to melting of TMDSC scan‐induced secondary crystals. PHB underwent considerable secondary crystallization/annealing that took place under modulated cooling conditions. The overall melting behavior was interpreted in terms of recrystallization and/or annealing of crystals. Interestingly, the PHB analyzed by temperature modulation programs showed a broad exotherm before the melting peak in the nonreversing heat capacity curve and a multiple melting reversing curve, verifying that the melting–recrystallization and remelting process was operative. WAXRD and POM studies supported the correlations from DSC and TMDSC results. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 70–78, 2006     

Melting of polymers by non-isothermal, temperature-modulated calorimetry: analysis of various irreversible latent heat contributions to the reversing heat capacity

This paper provides an analysis of contributions to the apparent, reversing heat capacity when measured by temperature-modulated differential scanning analysis (TMDSC) with an underlying heating rate in the temperature range where irreversible transitions with latent heats occur. To deconvolute the data of a TMDSC scan into a total and reversing part, it is common practice to use the sliding averages and the first harmonics of the Fourier series of temperature and heat-flow rate. Under certain conditions, this procedure produces erroneous reversing contributions which are detailed by experiment and simulation. Unless the response to the temperature modulation is linear, the total heat-flow rate is stationary, and the transition is truly reversible and occurs only once during the temperature scan, one cannot expect a true deconvolution of total and reversible effects. In the presence of multiple, irreversible transitions within a modulation period, however, each process involving latent heat can increase the modulation amplitude, as demonstrated by computer-simulation of polymer melting. As a result, the multiple transitions may give erroneously high latent heats when integrating the apparent reversing heat capacity with respect to temperature.     

Characterization of crystalline and amorphous content in pharmaceutical solids by dielectric thermal analysis

Morphological and thermodynamic transitions in drugs as well as their amorphous and crystalline content in the solid state have been distinguished by thermal analytical techniques, which include dielectric analysis (DEA), differential scanning calorimetry (DSC), and macro-photomicrography. These techniques were used successfully to establish a structure versus property relationship with the United States Pharmacopeia standard set of active pharmaceutical ingredient (API) drugs. A distinguishing method is the DSC determination of the amorphous and crystalline content which is based on the fusion properties of the specific drug and its recrystallization. The DSC technique to determine the crystalline and amorphous content is based on a series of heat and cool cycles to evaluate the drugs ability to recrystallize. To enhance the amorphous portion, the API is heated above its melting temperature and cooled with liquid nitrogen to ?120 °C (153 K). Alternatively a sample is program heated and cooled by DSC at a rate of 10 °C min^?1. DEA measures the crystalline solid and amorphous liquid API electrical ionic conductivity. The DEA ionic conductivity is repeatable and differentiates the solid crystalline drug with a low conductivity level (10^?2 pS cm^?1) and a high conductivity level associated with the amorphous liquid (10⁶ pS cm^?1). The DSC sets the analytical transition temperature range from melting to recrystallization. However, analysis of the DEA ionic conductivity cycle establishes the quantitative amorphous and crystalline content in the solid state at frequencies of 0.10–1.00 Hz and to greater than 30 °C below the melting transition as the peak melting temperature. This describes the “activation energy method.” An Arrhenius plot, log ionic conductivity versus reciprocal temperature (K^?1), of the pre-melt DEA transition yields frequency dependent activation energy (E _a, J mol^?1) for the complex charging in the solid state. The amorphous content is inversely proportional to the E _a where the E _a for the crystalline form is higher and lower for the amorphous form with a standard deviation of ±2%. There was a good agreement between the DSC crystalline melting, recrystallization, and the solid state DEA conductivity method with relevant microscopic evaluation. An alternate technique to determine amorphous and crystalline content has been established for the drugs of interest based on an obvious amorphous and crystalline state identified by macro-photomicrography and compared to the conductivity variations. This second “empirical method” correlates well with the “activation energy” method.     

Reversible Melting During Crystallization of Polymers Studied by Temperature Modulated Techniques (TMDSC, TMDMA)

Quasi-isothermal temperature modulated DSC and DMA measurements (TMDSC and TMDMA, respectively) were performed to determine heat capacity and shear modulus as a function of time during crystallization. Non-reversible and reversible phenomena in the crystallization region of polymers can be observed. The combination of TMDSC and TMDMA yields new information about local processes at the surface of polymer crystals, like reversible melting. Reversible melting can be observed in complex heat capacity and in the amplitude of shear modulus in response to temperature perturbation. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for PCL PET and PEEK. This shows that also after long crystallization times the surfaces of the individual polymer crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are ‘living crystals’. This revised version was published online in August 2006 with corrections to the Cover Date.     

Reversible and irreversible heat capacity of poly(trimethylene terephthalate) analyzed by temperature‐modulated differential scanning calorimetry

The heat capacity of poly(trimethylene terephthalate) (PTT) has been analyzed using temperature‐modulated differential scanning calorimetry (TMDSC) and compared with results obtained earlier from adiabatic calorimetry and standard differential scanning calorimetry (DSC). Using quasi‐isothermal TMDSC, the apparent reversing and nonreversing heat capacities were determined from 220 to 540 K, including glass and melting transitions. Truly reversible and time‐dependent irreversible heat effects were separated. The extrapolated vibrational heat capacity of the solid and the total heat capacity of the liquid served as baselines for the analysis. As one approaches the melting region from lower temperature, semicrystalline PTT shows a reversing heat capacity, which is larger than that of the liquid, an observation that is common also for other polymers. This higher heat capacity is interpreted as a reversible surface or bulk melting and crystallization, which does not need to undergo molecular nucleation. Additional time‐dependent, reversing contributions, dominating at temperatures even closer to the melting peak, are linked to reorganization and recrystallization (annealing), while the major melting is fully irreversible (nonreversing contribution). © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 622–631, 2000     

Data Analysis Without Fourier Transformation for Sawtooth-type Temperature-modulated DSC

The response of a differential scanning calorimeter (DSC) to sawtooth-type temperature modulation has been analyzed in the time domain using a standard treatment of the DSC data without Fourier transformation into the frequency domain. This method has some of the advantages of a temperature-modulated DSC (TMDSC) and may achieve a reasonable accuracy with more transparent and less time-consuming data analysis than the current TMDSC. The limits of linearity and stationarity of the thermal response, a prerequisite for the validity of the calculation of the reversing heat capacity by Fourier transformation, can be easily recognized in standard DSC. In contrast to the common handling of TMDSC, where the non-reversing contributions are calculated as difference between the total and reversing parts, we define a new, directly measured quantity, called the imbalance in heat capacity. It represents the difference between heating and cooling due to the non-reversing thermal process. This quantity is also of value for the representation of irreversible contributions inquasi-isothermal processes, such as cold crystallization and the annealing of crystallites in the melting range. This revised version was published online in July 2006 with corrections to the Cover Date.     

Temperature‐modulated differential scanning calorimetry studies on the origin of double melting peaks in isothermally melt‐crystallized poly(L‐lactic acid)

In this work, the melting behaviors of nonisothermally and isothermally melt‐crystallized poly(L ‐lactic acid) (PLLA) from the melt were investigated with differential scanning calorimetry (DSC) and temperature‐modulated differential scanning calorimetry (TMDSC). The isothermal melt crystallizations of PLLA at a temperature in the range of 100–110 °C for 120 min or at 110 °C for a time in the range of 10–180 min appeared to exhibit double melting peaks in the DSC heating curves of 10 °C/min. TMDSC analysis revealed that the melting–recrystallization mechanism dominated the formation of the double melting peaks in PLLA samples following melt crystallizations at 110 °C for a shorter time (≤30 min) or at a lower temperature (100, 103, or 105 °C) for 120 min, whereas the double lamellar thickness model dominated the formation of the double melting peaks in those PLLA samples crystallized at a higher temperature (108 or 110 °C) for 120 min or at 110 °C for a longer time (≥45 min). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 466–474, 2007     

Experimental Considerations for Temperature Modulated DSC at Low Temperature

Temperature modulated DSC (TMDSC) at low temperatures requires attention to the selection of experimental parameters that are within the capability of the instrumentation as well as special care in calibration of heat capacity measurement when high precision is required. Data are presented to facilitate selection of appropriate modulation periods and amplitudes at low temperature when using a mechanical cooling accessory. The standard error of the mean heat capacity measurement for a sapphire standard increased with decreasing temperature, decreasing period, and increasing pan mass. For ice in hermetically sealed pans, the standard error of the mean heat capacity measurement was larger than for sapphire and did not follow a predictable trend with changes in temperature and period of modulation. This was attributed to changes in sample geometry between successive measurements due to melting and resolidification. A simple one-point temperature calibration by TMDSC may be unsuitable for precise measurement of heat capacity because of the random error caused by sample placement and the systematic error caused by cell asymmetry, temperature dependence of the calibration constant, and different sample thermal conductivities. An alternative calibration procedure using standard DSC and either a linear or second order fit of the calibration constant over the temperature range of interest is proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effects of carbon nanotubes on crystallization and melting behavior of poly(L‐lactide) via DSC and TMDSC studies

In this work, multiwalled carbon nanotubes (MWNTs) were surface‐modified and grafted with poly(L ‐lactide) to obtain poly(L ‐lactide)‐grafted MWNTs (i.e. MWNTs‐g‐PLLA). Films of the PLLA/MWNTs‐g‐PLLA nanocomposites were then prepared by a solution casting method to investigate the effects of the MWNTs‐g‐PLLA on nonisothermal and isothermal melt‐crystallizations of the PLLA matrix using DSC and TMDSC. DSC data found that MWNTs significantly enhanced the nonisothermal melt‐crystallization from the melt and the cold‐crystallization rates of PLLA on the subsequent heating. Temperature‐modulated differential scanning calorimetry (TMDSC) analysis on the quenched PLLA nanocomposites found that, in addition to an exothermic cold‐crystallization peak in the range of 80–120 °C, an exothermic peak in the range of 150–165 °C, attributed to recrystallization, appeared before the main melting peak in the total and nonreversing heat flow curves. The presence of the recrystallization peak signified the ongoing process of crystal perfection and, if any, the formation of secondary crystals during the heating scan. Double melting endotherms appeared for the isothermally melt‐crystallized PLLA samples at 110 °C. TMDSC analysis found that the double lamellar thickness model, other than the melting‐recrystallization model, was responsible for the double melting peaks in PLLA nanocomposites. Polarized optical microscopy images found that the nucleation rate of PLLA was enhanced by MWNTs. TMDSC analysis found that the incorporation of MWNTs caused PLLA to decrease the heat‐capacity increase (namely, ΔC_p) and the C_p at glass transition temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1870–1881, 2007     

Temperature-modulated calorimetry of hexacontane and oligomer fractions of poly(oxyethylene) and poly(oxytetramethylene)

The paraffin hexacontane, C₆₀H₁₂₂, and oligomeric fractions of poly(oxyethylene), POE, and poly(oxytetramethylene), POTM, of varying low molar masses were studied with temperature-modulated calorimetry. The analyses were by standard differential scanning calorimetry (DSC) and quasi-isothermal, temperature-modulated DSC, TMDSC. Small sample masses were examined with temperature amplitudes from 0.05 to 2.5 K, using periods of 60 s. The supercooling decreases with molar mass for all three types of samples. The melting varied between fully irreversible, reversing, and largely reversible. There are no major differences in supercooling between extended- and folded-chain crystals. Due to conformational contributions, all crystals increase their heat capacities within the melting range from the level set by the vibrational spectrum to that of the liquid.     

Preparation,Characterization and Thermal Energy Storage Properties of Micro/Nano Encapsulated Phase Change Material with Acrylic-Based Polymer

The eutectic mixture of octacosane (C28)–heptadecane (C17) as core material was successfully encapsulated with an acrylic-based polymer (polymethylmethacrylate; PMMA) as shell material through emulsion polymerization. The polymeric reaction occurred around the core material was characterized by FTIR spectroscopy analysis. The polarized optical microscopy, scanning electron microscopy and particle size distribution investigations showed that the most of the prepared capsules had almost spherical shape with non-unimodal size distribution in micro-nano range. The differential scanning calorimetry analysis results exhibited that the capsules including highest amount of the eutectic PCM had a melting temperature of about 21°C and a latent heat capacity of about 98 J/g. The high thermal durability of the prepared capsules was confirmed by thermogravimetric analysis. The thermal cycling test designated that the synthesized capsules had good long-term usage latent heat thermal energy storage (LHTES) performance and chemical stability. Furthermore; the fabricated capsules with (1: 2) shell/core ratio had a reasonable thermal conductivity. It can be drawn a conclusion from all results that the prepared capsules especially PMMA/(C28–C17) (1: 2) product is a hopeful PCM that can be evaluated for low-temperature LHTES applications.     

Thermal and thermomechanical properties of poly[(butylene succinate)-co-adipate] nanocomposite

In this article the thermal and thermomechanical properties of neat poly[(butylene succinate)-co-adipate] (PBSA) and its nanocomposite are reported. Nanocomposite of PBSA with organically modified synthetic fluorine mica (OSFM) has been prepared by melt-mixing in a batch mixer. The structure of nanocomposite is characterized by X-ray diffraction patterns and transmission electron microscopic (TEM) observations that reveal homogeneous dispersion of intercalated silicate layers in the PBSA matrix. The melting behavior of pure polymer and nanocomposite samples are analyzed by differential scanning calorimetry (DSC), which shows multiple melting behavior of the PBSA matrix. The multiple melting behavior of the PBSA matrix is also studied by temperature modulated DSC (TMDSC) and wide-angle XRD (WXRD) measurements. All results show that the multiple melting behavior of PBSA is due to the partial melting, re-crystallization, and re-melting phenomena. The investigation of the thermomechanical behavior is performed by dynamic mechanical thermal analysis. Results demonstrate substantial enhancement in the mechanical properties of PBS, for example, at room temperature, storage flexural modulus increased from 0.5 GPa for pure PBS to 1.2 GPa for the nanocomposite, an increase of about 120% in the value of the elastic modulus. The thermal stability of nanocomposite compared to that of neat PBSA is also examined in pyrolytic and thermo-oxidative conditions. It is then studied using kinetic analysis. It is shown that the stability of PBSA is increased moderately in the presence of OSFM.     

Analysis of the complex thermal behavior of poly(L‐lactic acid) film. I. Samples crystallized from the glassy state

The melting behavior of poly(L ‐lactic acid) film crystallized from the glassy state, either isothermally or nonisothermally, was studied by wide angle X‐ray diffraction (WAXD), small angle X‐ray scattering (SAXS), differential scanning calorimetry (DSC), and temperature‐modulated differential scanning calorimetry (TMDSC). Up to three crystallization and two melting peaks were observed. It was concluded that these effects could largely be accounted for on the basis of a “melt‐recrystallization” mechanism. When molecular weight is low, two melting endotherms are readily observed. But, without TMDSC, the double melting phenomena of high molecular weight PLLA is often masked by an exotherm just prior to the final melting, as metastable crystals undergo melt‐recrystallization during heating in the DSC. The appearance of a double cold‐crystallization peak during the DSC heating scan of amorphous PLLA film is the net effect of cold crystallization and melt‐recrystallization of metastable crystals formed during the initial cold crystallization. Samples cold‐crystallized at 80 and 90 °C did not exhibit a long period, although substantial crystallinity developed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3200–3214, 2006     

Melting and crystallization of poly(butylene terephthalate) by temperature‐modulated and superfast calorimetry

Quantitative temperature‐modulated differential scanning calorimetry (TMDSC) and superfast thin‐film chip calorimetry (SFCC) are applied to poly(butylene terephthalate)s (PBT) of different thermal histories. The data are compared with those of earlier measured heat capacities of semicrystalline PBT by adiabatic calorimetry and standard DSC. The solid and liquid heat capacities, which were linked to the vibrational and conformational molecular motion, serve as references for the quantitative analyses. Using TMDSC, the thermodynamic and kinetic responses are separated between glass and melting temperature. The changes in crystallinity are evaluated, along with the mobile–amorphous and rigid–amorphous fractions with glass transitions centered at 314 and 375 K. The SFCC showed a surprising bimodal change in crystallization rates with temperature, which stretches down to 300 K. The earlier reported thermal activity at about 248 K was followed by SFCC and TMDSC and could be shown to be an irreversible endotherm and is not caused by a glass transition and rigid–amorphous fraction, as assumed earlier. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1364–1377, 2006