DSC Investigation of some Testing and Calibration Compounds, Particularly During Cooling

Two compounds are described with interesting properties for use in DSC. The first compound is adamantane (C₁₀H¹⁶), with a reversible solid-solid transition at 208.62 K [1], suitable for DSC calibration at this low temperature [2]. The second compound is 4,4'-azoxyanisole (C₁₄H₁₄N₂O₃), with a liquid crystal range between 390 and 407 K [3]. This compound shows two transitions on heating, with a large heat effect at 390 K and a small heat effect at 407 K. For this reason, this substance is well suitable for testing the sensitivity and the resolution of DSC instruments [4]. For both compounds not only the heating, but also the cooling behaviour is investigated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.     

Melting and high-temperature solid state transitions in cobalt(II) halides

Melting and high temperature solid-state transitions in CoCl₂ and CoBr₂ are widely discussed. On the basis of DSC and conductometric measurements it was found that melting process of CoCl₂ is preceded by a solid-state transition appearing about 20 K below the melting point of CoCl₂. Due to deconvolution of the thermograms, the enthalpy of fusion and that of solid-state transition were found to be 36.4 and 9.6 kJ mol^–1, respectively. Melting points of CoCl₂ and CoBr₂ were established to be 999.0 and 949.7 K, respectively. Hitherto unknown enthalpy of fusion of CoBr₂ was determined to be 27.2 kJ mol^–1. A solid-state transition in CoBr₂ at 650 K has been confirmed.     

Specific heat capacity and melting/crystallization characteristics of polytridecanolactone

An investigation of the thermodynamical properties of polytridecanolactone (PTDL) was made with the aid of a differential scanning calorimeter (DSC). PTDL is a linear polyester and belongs to the polylactones, which have been poorly investigated. In this paper we contribute with specific heat capacity in the range 180-400 K, and melting and glass transition characteristics. Further, we present unique results corresponding to the effect of different cooling rates on crystallization temperatures and crystallization energies. PTDL has a melting temperature of 350 K, and a glass transition at about 237 K. The crystallization results show that PTDL crystallizes easily, with a crystallization degree of about 80%. In addition, the crystallization energy decreases with increasing cooling rate, and levels out at a constant value at higher cooling rates. The crystallization temperature, on the other hand, shows an increasing sensitivity of cooling rate, where the supercooling is increasing more rapidly at higher cooling rates. © 1994 John Wiley & Sons, Inc.     

Differential scanning calorimetry study on thermal behaviors of freeze‐dried poly(L‐lactide) from dilute solutions

Glass transition, cold crystallization, and melting of freeze‐dried poly(L‐lactide) (PLLA) prepared from dilute 1,4‐dioxane solutions were investigated by differential scanning calorimetry (DSC). Conventional DSC measurements of heating scans revealed that freeze‐dried PLLA prepared from a 0.07 wt % solution undergoes a two‐step cold crystallization (or reorganization) with a lower exotherm appearing at about 78 °C and with a higher broad exotherm between 110–155 °C. The peak temperature of the former exotherm is about 50 K lower than that observed for a reference bulk sample. Step‐scan mode DSC, which provides information essentially equivalent to that obtained from the temperature‐modulated DSC, revealed that the glass‐transition temperature is about 6 K lower than that of the reference bulk. These findings suggest enhanced chain mobility for freeze‐dried PLLA. Freeze‐dried PLLA that crystallized at 80 °C for 40 min was revealed to contain a rather large amount of rigid amorphous material (42%). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 115–124, 2005     

Study on melting and polymorphic behavior of poly(decamethylene terephthalamide)

This work describes the melting and polymorphic behavior of poly(decamethylene terephthalamide) (PA 10T). Both solution‐crystallized (SC) and melt‐crystallized (MC) PA 10T show double melting endotherms in DSC. The SC crystal form melts at 260–300°C giving the first melting endotherm, and meanwhile undergoes a polymorphic transition forming the MC crystal form. The subsequent melting of the MC crystal form gives the second melting endotherm at 300–325°C. This irreversible polymorphic transition is confirmed by variable‐temperature WAXD and IR. Dynamic mechanical thermal analysis (DMTA) shows a glass transition temperature (T_g) at 127°C and the presence of an α′ transition at 203°C (0.1 and 1 Hz). This transition could be confirmed by DSC and variable‐temperature WAXD experiments. The α′ transition correlates with a reversible thermal process and a sudden change in intersheet spacing. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 465–472     

Phase Diagram of Gelatin Plasticized by Water and Glycerol

Summary: Gelatin is widely used in capsules manufacturing. Most of the capsules in pharmaceutical applications are hard capsules made out of concentrated solutions of gelatin, where water has been progressively removed during the drying process. More recently soft capsules found an increasing interest in pharmaceutical and cosmetic applications where they are filled and sealed with a liquid substance. In order to keep the shells of capsules flexible after drying at room temperature, plasticizer is added to the gelatin aqueous solutions. We present in this paper a systematic investigation of gelatin films, equilibrated under a range of relative humidity (RH). The films contain glycerol as plasticizer P or only water and gelatin, (G). In order to analyze the role of the plasticizer, we fixed various P/G ratios and measured the water retention versus RH. Films were characterized by DSC (Mettler Toledo DSC823). Glass transition temperature T_g, melting temperature T_m and enthalpy associated with helix-coil transition were determined. The role of water and glycerol was examined in relation with the large variations of these transition temperatures with film composition. Non equilibrium effects are also discussed, in particular concerning the glass transition temperature, the relaxation effects and the water repartition between amorphous coils and helical structure. In conclusion, we propose a unique phase diagram of the gelatin films with any proportion of water and glycerol.     

An Electric Criterion to Evaluate Glass Transition Temperature: Dielectric Relaxation Measurements

In this contribution, a dielectric measurement technique for the evaluation of phase transition temperature and the study of physical aging on polymeric thin films is considered. This kind of measurement provides the possibility of displaying phase transitions with a high degree of precision. Furthermore, it can be considered alternatively to techniques not applicable in the case of thin films, such as Differential Scanning Calorimetry (DSC). In this work, owing to the high sensitivity of the utilized experimental set-up, a glass transition T_G of 156 K, with a precision equal to 0.3%, and a melting T_M = 220 K have been assessed for 4 µm thick Polydimethylsiloxane (PDMS) films. Performing measurement as a function of time, it was possible to monitor physical aging phenomena, mainly consisting in a change of dielectric properties. As expected, the time evolution of the aging phenomena can be described by a simple logarithmic law.     

Crystallization behavior and morphology of poly(butylene succinate) modified with rosin maleopimaric acid anhydride

The melting behavior, crystallization behavior, and morphology of PBSR, which is Poly(butylene succinate) modified with rosin maleopimaric acid anhydride (RMA), were investigated with differential scanning calorimetry (DSC) and polarized optical microscope (POM). The multiple endotherms were ascribed to the recrystallization during DSC measurement and the equilibrium melting temperature determined by the Peak L, which was associated with the fusion of the crystals grown by normal primary crystallization, was 125.9 °C. After the kinetic parameters for isothermal crystallization of PBSR were determined by Avrami equation, to make a detailed regime transition analysis, the well‐established Lauritzen–Hoffman equation was employed. The results indicated that there were two regimes, regime II and regime III, in the range of higher and lower crystallization temperature, respectively. The regime transition temperature is about 81 °C. At last, the spherulitic morphologies of PBSR after being crystallized isothermally at different temperature were observed with the help of POM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2694–2704, 2005     

Crystallization and melting of a branched polyethylene with precisely controlled chemical structure

The heat capacity of a linear polyethylene with dimethyl branches, at every 21st backbone atom was analyzed by differential scanning calorimetry (DSC) and quasi-isothermal temperature-modulated DSC. This novel copolyethylene (PE2M) is relatively difficult to crystallize from the melt. On subsequent heating, a first, sharp melting peak is followed by a sharp cold-crystallization and crystal perfection and a smaller endotherm, before reaching the main melting at 315–320 K, close to the melting temperatures of eicosane and tetracontane. The low-temperature melting is sensitive to the cooling rate and disappears below 1.0 K min⁻¹. The cold crystallization can be avoided by heating with rates faster than 80 K min⁻¹. The PE2M exhibits some reversing and reversible melting, which is typical for chain-folded polymers. The glass transition of semicrystalline PE2M is broadened and reaches its upper limit at about 260 K (midpoint at about 0.355 K). Above this temperature, the crystals seem to have a heat capacity similar to that of the liquid. A hypothesis is that the melting transition can be explained by changes in crystal perfection without major alteration of the crystal structure and the lamellar morphology. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3461–3474, 2006     

Thermal behavior and polymorphism in medium–high temperature range of the sulfur containing amino acids <Emphasis Type="SmallCaps">l</Emphasis>-cysteine and <Emphasis Type="SmallCaps">l</Emphasis>-cystine

A thermophysical study of the sulfur containing amino acids l-cysteine and l-cystine has been carried out by differential scanning calorimetry (DSC). Heat capacities of both compounds were measured in the temperature interval from T = 268 K to near their respective melting temperatures. DSC and variable temperature powder X-ray diffraction analysis (PXRD) gave evidence for a solid–solid phase transition close to the melting point only in the l-cysteine sample. DSC experiments show that this solid–solid transition is not reversible in the temperature interval T = 235–485 K and presents a behavior depending on heating temperature, time, and rate. This behavior is also supported by variable-temperature PXRD. The patterns for the commercial samples, at room temperature, are consistent with those simulated for the orthorhombic and hexagonal polymorphic forms from the single-crystal X-ray analysis.     

Temperature-triggered phase transition in pyridazine hexafluorophosphate

The pyndazine hexafluorophosphate[C₄H₅N₂]⁺[PF₆]^-（1） undergoes a reversible phase transition around140 K,which was confirmed by the DSC measurement.Variable-temperature crystal structures determined at 293 K and 93 K show that the compound crystallizes in the same space group P2₁/c,indicating that 1 undergoes an iso-structural phase transition.As the temperature decreases,dielectric measurement of the title compound shows no significant change around the phase transition temperature.Classic hydrogen bonds are found between molecules at 293 K and 93 l< with similar packing arrangement.The most distinct difference between the low temperature and room temperature structures is the order-disorder transition of the hexafluorophosphate anion,which is probably the driving force of the phase transition.     

Heat capacity functions of polystyrene in glassy and in liquid amorphous state and glass transition

The heat capacity or the specific heat is for any crystalline, partially amorphous or completely amorphous substance or material a significant thermodynamic property. The glass transition may be regarded as the melting point of amorphous substances and materials, a transition property of an outstanding technical importance. A crucial point is the fact that the presence of a glass transition is an unequivocal proof of an amorphous content of a material. Furthermore, the change of the specific heat at the glass transition temperature enables the quantitative determination of the amorphicity on a relative or absolute level of any substance or material. The absolute determination of the amorphicity affords a calibration with a reference corresponding to the material under investigation. The crystallinity for this reference substance must be known from the preparation and or by any independent analytical method. The literature data for the specific heat and the glass transition of polystyrene were collected and evaluated. Data were found for the specific heat in literature from 10 to 470 K. The data were unified for each of the reported temperature in a mean value and the corresponding standard deviation was determined. An excellent conformity was found in the glassy state of polystyrene with standard deviations lower than 0.7%. The standard deviations above the glass transition were considerably higher.     

2-氨基-4，6-二甲氧基嘧啶的低温热容和热力学性质研究

通过精密自动绝热量热计测定了自行合成并提纯的2-氨基-4，6-二甲氨基嘧啶 在78-394 K温区的摩尔热容。实验结果表明，该化合物有一个固-液溶化相变，其 熔化温度、摩尔熔化焓以及摩尔熔化熵分别为：（370.97 ± 0.02）K，（29853. 91 ± 9.25） J·mol~(-1)和（80.45 ± 0.03）J·mol~(-1) · K~(-1)。通过分 步熔化法得到样品的纯度为0.9984 (摩尔分数)和绝对纯样品的熔点为371.031 K。 在热容测量的基础上计算出了该物质每隔5K的热力学函数值。DSC技术对基固-溶熔 化过程作了进一步研究，结果与热容试验相一致。     

Crystal modifications and multiple melting behavior of poly(L‐lactic acid‐co‐D‐lactic acid)

The crystal modifications and multiple melting behavior of poly(L ‐lactic acid‐co‐D ‐lactic acid) (98/2) as a function of crystallization temperature were studied by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). It was found that the disorder (α′) and order (α) phases of poly(L ‐lactic acid) (PLLA) were formed in cold‐crystallized poly(L ‐lactic acid‐co‐D ‐lactic acid) samples at low (<110 °C) and high (≥110 °C) temperatures, respectively. A disorder‐to‐order (α′‐to‐α) phase transition occurred during the annealing process of the α′‐crystal at elevated temperatures, which proceeded quite slowly even at the peak temperature of the exotherm P_exo but much more rapidly at higher temperature close to the melting region. The presence or absence of an additional endothermic peak before the exotherm in the DSC thermograph of the α′‐crystal was strongly dependent on the heating rate, indicating that a melting process involved during the α′‐to‐α phase transition. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Rheological and thermal properties of a commercial liquid-crystalline polyesteramide

A commercial main-chain liquid-crystalline, naphthalene-based polyesteramide, was studied by three experimental techniques: extrusion capillary rheometry, dynamic viscoelasticity, and differential scanning calorimetry (DSC). From capillary rheometry a maximum at 360°C was observed in viscosity temperature curve. This result is compared with literature data for other thermotropics, and the possibility of a transition from a nematic to an isotropic phase is considered. The results obtained from dynamic viscoelasticity and DSC agree, and reveal the existence of a glass transition at 128°C (by DSC) and 137–147°C (by viscoelastic measurements, depending on frequency) as well as melting at 282°C. Annealing below 230°C produces two types of crystals, whereas annealing above this temperature gives rise to only one type of crystal, the melting temperature of which can be, depending on annealing time, as high as 340°C. The results are compiled in a phase diagram with six regions, four of them corresponding to the solid state, one to a liquid mesophase, and one to an isotropic phase.     

A combined photoacoustic DSC for simultaneous temperature modulated measurements: does it really work?

Combination of two techniques, photoacoustic (PA) and differential scanning calorimetry (DSC), is a combination of quasi stationary thermodynamic DSC method and nonstationary dynamic PA method. Especially favorable and easy to realize is the combination with power compensated type of DSC. It has several advantages over the use of two techniques separately and allow to perform measurements simultaneously. The most obvious is simultaneous determination of thermodynamic properties such as specific heat, heat of transition and dynamic properties such as effusivity, thermal conductivity at the different phase transitions and complex specific heat at the glass transition. Unlike other temperature modulated techniques PA–DSC is especially suitable for studying polymer materials since their low thermal conductivity is an additional advantage. Conditions for simultaneous measurements are examined. It is proved that the combination of two techniques and necessary changes in construction do not essentially change adequate work of the instrument. A little disbalance of DSC operation due to the construction change can be corrected simply by recalibration. The procedures for testing and calibration for the proper operation of the combined PA–DSC are given together with some details of experimental methodology. Several measurements could serve as examples of widespread applicability of PA–DSC to study different types of phase transitions as well as time dependent processes such as glass transition.     

Optimization of instrument response and resolution of standard- and high-speed power compensation DSC

Normally, for Standard DSC, the PerkinElmer power-compensation setting is the low dynamic range mode (LDRM). In this mode, a noise filter is applied to decrease the noise-to-signal ratio, which concomitantly gives rise to a delay in time of the signal measured. In case the signal is expected to be of high intensity — experienced for instance at high scan rates using High Performance DSC (HPer DSC) — the noise filtering could be diminished by which the associated delay in time would be less, leading to a faster response of the instrument, also resulting in an improved resolution. In fact, such can be realized using the faster noise filter of the high dynamic range mode (HDRM) available for the Pyris 1 and Diamond DSCs, which DSCs are both equipped with the HyperDSC^TM technique (HyperDSC being the commercial version of HPer DSC). The improvement in response is maximal for high rates like 100–500°C min⁻¹ but even at low rates like 10°C min⁻¹ it is still significant. Thus, taking advantage of HDRM, low-molar substances like indium and 4,4′-azoxyanisole show appreciable increasing height-to-width ratios for signals caused by crystallization, melting and the crystal <>liquid crystal transition respectively. Another advantage, the faster realization of steady state after the starting of the DSC, is of help in case of overlapping starting and transition signals during dynamic crystallization and melting, and during isothermal crystallization as elucidated for a HDPE. For 4,4′-azoxyanisole and for an ethylene-propylene copolymer having a broad melting range, it is shown that such faster response leads to a still better resolution with respect to temperature, even at high scan rates. Thus, the peaks belonging to the crystal-to-liquid crystal and the liquid crystal-to-isotropic liquid transitions of 4,4′-azoxyanisole were completely resolved while a thermal fractionation of the copolymer by the successive self-nucleation and annealing (SSA) technique with good resolution has been realized, both using rates as high as 200°C min⁻¹.     

The effect of oxygen content on the melting of the eutectic of physiological salinity solution

The effect of oxygen concentration on the melting of this eutectic was investigated by DSC. In the deoxygenized solution, an endothermic peak attributed to the eutectic transition was observed in the course of heating, and its peak temperature is around ?21.5°C. Another endothermic peak appeared at lower temperature in the presence of oxygen. As the oxygen content in the solution increases, the temperature of this peak is shifted to lower temperature. The transition at the lower temperature are associated with the melting of eutectic carrying oxygen. The same results are given in the NMR data.