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Homogeneous crystal nucleation in polyamide 66 (PA 66) was studied by a combination of atomic-force microscopy (AFM) and fast-scanning chip calorimetry (FSC), with a specific experimental setup all...

Kinetic methods have been widely used in analytical chemistry, generally using spectrophotometric or electrochemical detector. However, although enthalpimetric methods have been scarcely used, they may offer some interesting performances, like to be blind to the color and/or turbidity of the samples. This paper will be related with the description of some enthalpimetric kinetic methods and their instrumentation that could be used in these techniques, making a review on direct injection catalytic enthalpimetry, thermometric titration with catalytic endpoint detection, catalytic enthalpimetric flow injection analysis, continuous flow enthalpimetries, chip calorimetry, and trends of kinetic thermometric detection.

The effect of molar mass on the reorganization behavior of α′-crystals of poly ( l -lactic acid) (PLLA) has been investigated by fast scanning chip calorimetry. The α′-crystals of PLLA were formed by isothermal crystallization of the relaxed melt at 90 °C or lower temperatures, and were then heated at different rates between 2 and 200 K s − 1 . Slow heating permits for all PLLA samples of different molar mass between 2 and 576 kDa reorganization of α′- into α-crystals. It was found that the α′/α-transition is suppressed if heating occurs faster than 10 K s − 1 in case of the sample with a molar mass of 576 kDa, while the critical heating rate to suppress the formation of α-crystals is increased to 30 and 100 K/s in PLLA with molar masses of around 100 kDa and 2 kDa, respectively. The faster kinetics of the α′/α-transition in case of shorter macromolecules may be explained by faster melting of smaller α′-crystals, faster growth of α-crystals from the non-isotropic melt containing remnants/self-seed from molten α′-crystals, and/or a higher number of such α′-crystal remnants/self-seed.

Melting of original crystals and their recrystallization during heating were successfully separated for isothermally crystallized poly(butylene terephthalate) (PBT). The corresponding kinetics was determined and quantitatively discussed for a wide range of heating rates (0.1–100,000 K s -1 ) using fast-scanning chip calorimetry (FSC) and differential scanning calorimetry (DSC). The double melting peaks observed on the FSC curves are assigned to the melting of original crystals (low-temperature peak) and recrystallized and/or reorganized crystals (high-temperature peak). Heating rate dependence of the degree of recrystallization has been evaluated and the kinetics was discussed on the basis of Ozawa's method. Compared with the melt-crystallization and cold-crystallization, recrystallization kinetics is the fastest process. This is because many crystal remnants, which do not transform into the isotropic melt, act as athermal nuclei, and accelerate recrystallization.

The efficiency of linear trans γ-quinacridone to nucleate formation of β-crystals in isotactic polypropylene (iPP) at rapid cooling conditions has been evaluated by a combination of fast scanning chip calorimetry (FSC) and microfocus wide-angle X-ray scattering (WAXS). For samples containing different amount of γ-quinacridone, FSC cooling experiments revealed information about a critical cooling rate above which the crystallization temperature decreases to below 105 °C, that is, to temperatures at which the growth rate of α-crystals is higher than that of β-crystals. Microfocus WAXS analysis was then applied to gain information about the competition of formation of β- and α-crystals in samples prepared at well-defined conditions of cooling at rates up to 1000 K/s in the FSC. For iPP containing 1 and 500 ppm γ-quinacridone, the crystallization temperature is lower than 105 °C on cooling faster about 10 and 70 K/s, respectively, which then on further increase of the cooling rate leads to a distinct reduction of the β-crystal fraction. The study may be considered as a first successful attempt to quantify and interpret β-crystal formation in iPP containing γ-quinacridone at processing-relevant cooling conditions in the shed of light of the different temperature-dependence of the growth rates of α- and β-crystals.

Fast scanning chip calorimetry in its non-adiabatic version allows for heating and cooling at rates up to 106 K s−1, covering all polymer processing relevant rates. Furthermore it allows for systematic studies of nucleation, crystallization, melting and reorganization for a large number of polymers. After an introduction, open problems and the need for further investigation of polymer crystallization are explained, followed by a brief description of the novel technique of fast scanning chip calorimetry and its capability to shed further light on fundamental details of the polymer-crystallization process. In the fourth part, specific examples of non-isothermal and isothermal crystallization studies are provided, including the discussion of the effect of nucleating agents. The possibility to investigate homogeneous nucleation and its kinetics is highlighted too. The fifth part focuses on the analysis of the melting kinetics and the determination of the zero-entropy-production melting temperature.

Smart detection systems for explosive sensors are designed both to detect explosives in the air at trace level and identify the threat for a specific response. Following this need we have succeeded in using microthermal analysis to sensitively identify and discriminate between RDX and PETN explosive vapors at trace level. Once the explosive vapor is trapped in a porous material, heating the material at a fast rate of 3000 K/s up to 350 °C will result in a thermal pattern specifically corresponding to the explosive and its interaction with the porous material. The explosive signatures obtained make it possible to simultaneously identify the presence and the nature of the explosive vapor in just a few milliseconds. Therefore, this also allows the development of multitarget devices using porous material for capturing the vapor combined with microthermal analysis for fast detection and identification. So far it is the first time that chip calorimetry has been used to characterize and identify explosives in vapor state.

A novel infrared (IR) thermo-spectroscopic imaging technique is applied to the simultaneous measurements of IR transmittance spectroscopic images and thermal emission images of heat and mass transfers of styrene monomer polymerization in microfluidics. The heat released is observed in the mixing layer between two laminar flows of styrene monomer and toluene containing an initiator for polymerization. The concentration of chemical species and the independently measured temperature distribution within the mixing layer are determined at the microscale. This is the first report, of such a non-invasive method, to determine both the chemical composition and temperature distribution in microfluidic chemical reactions.

It was reported that glass transition temperature (Tg) measured by differential alternating current (ac) chip calorimetry showed little thickness dependence for polymer films. Here we demonstrate the detection of Tg in thin films by ac-chip calorimeter and show that Tg is decreased as the thickness is reduced for oligomers and star-shaped polymers, as compared with their long linear analogues. The deviation range is a few to more than ten Kelvin. Such a depression in Tg is quite pronounced for ac-chip calorimetric measurement at a high frequency of 10 Hz. We argue that the perturbation in the increased interfacial free volume for spin-cast oligomers and dendrimers is the major reason for increasing segmental dynamics for ultrathin films.

The kinetics of crystal nucleation of poly(L-lactic acid) (PLLA) has been analyzed by fast scanning chip calorimetry in a wide temperature range between 313 and 383 K, that is, between temperatures about 30 K below and 40 K above the glass transition temperature. The relaxed melt was rapidly cooled to the analysis temperature and subsequently aged between 10 −1 and 10 4 s, to permit formation of nuclei. The number of formed crystal nuclei has been probed by analysis of the crystallization rate at 393 K. The nucleation rate is maximal at 370–375 K and decreases monotonously with decreasing temperature in the analyzed temperature range. The observation of a monomodal dependence of the nucleation rate on temperature points to predominance of a single nucleation mechanism in the analyzed temperature range, regardless nucleation occurs in the glassy or devitrified amorphous phase. The collected data suggest that nuclei formation at ambient temperature requires a waiting time longer than about 10 8 s. The performed study is considered as a quantitative completion of nucleation-rate data available for PLLA only at temperatures higher than 360 K, suggesting that the nucleation mechanism is independent on temperature in the analyzed temperature range between 313 and 383 K.

A combination of fast scanning chip calorimetry and X-ray ptychography is explored to study the effects of thermal annealing on the active layer of bulk heterojunction organic photovoltaics. The well-known P3HT/PC 61 BM 1:1 system is investigated as a test case. By using a custom chip calorimetry setup, it is possible to give a thermal treatment at 127 °C (400 K) to P3HT/PC 61 BM 1:1 thin layers, using a heating and cooling rate of 30000 K s −1 , after which the resulting morphology is investigated with X-ray ptychography. Applying only heating and cooling, without isothermal annealing, yields a featureless morphology. This corresponds well with thermal data which indicate a mixed amorphous phase only. For increasing isothermal annealing times, a well-defined morphology appears with increasing domain size, corresponding to the formation of an endothermal melting trajectory. This melting trajectory is expected to consist of both eutectic melting and melting of coarsened crystals. In contrast to chip calorimetry results, large domain sizes are obtained for heating and cooling without isothermal annealing at a conventional rate of 20 K min −1 . This initial morphology then develops further with increased isothermal annealing. The combination of chip calorimetry and ptychography allows separating the effects of each single thermal step on morphology development.

The phase separation behavior of polymer blend thin films of 100–150 nm was studied using differential AC Chip calorimetry. By taking advantage of the low sensor and sample mass inherent to chip calorimetry, a new methodology based on temperature jumps was developed. This methodology allowed the construction of the state diagram of polymer blend thin films as evidenced for two model systems (PVME/PS and PVME/Phenoxy) displaying a lower critical solution temperature behavior. The state diagram in thin films was compared to the one obtained in bulk using Modulated Temperature DSC. In comparison with bulk, a lower phase separation temperature and a broadening of the homogeneous glass transition temperatures is observed for both model systems. This might be an indication of a surface induced ‘destabilization’ by composition gradients which are not present in bulk.

The presented paper analyzes the potential of chip calorimetry for biochemical and cell biological investigations. From the thermo-physical properties of the heat power detectors of a chip calorimeter can be deduced that relevant applications mainly refer to fast reactions in extremely small samples. In contrast, the use of chip calorimeters for studying slow processes such as biochemical or microbial reactions is restricted. However, careful optimization of chip calorimeters concerning signal resolution and sample volume enables the investigation of enzymatically catalyzed reactions and the measurement of microbial growth heat as subsequently demonstrated with some typical examples from the literature.

The efficiency of γ-quinacridone to nucleate β-crystal formation in isotactic polypropylene (iPP) at rapid cooling has been evaluated by a combination of fast scanning chip calorimetry (FSC) and wide-angle X-ray scattering (WAXS). For samples with different amount of γ-quinacridone, FSC experiments revealed information about a critical cooling rate above which the crystallization temperature decreases to below 105 °C, that is, to temperatures at which the growth rate of α-crystals is higher than that of β-crystals. Microfocus WAXS analysis was then applied to gain information about the competition of formation of β- and α-crystals in samples prepared at defined cooling conditions at rates up to 1000 K/s in the FSC. For iPP containing 1 and 500 ppm γ-quinacridone, the crystallization temperature is lower than 105 °C on cooling faster about 10 and 70 K/s, respectively, which then on further increase of the cooling rate leads to a distinct reduction of the β-crystal fraction.

Thanks to the development of fast-scanning (chip-based) calorimeters (FSC) it is nowadays possible to achieve very high cooling rates, which enabled the study of polymer crystallization at large supercoolings, in conditions similar to what is experienced in real industrial processes. In such extreme conditions formation of structures very different from those commonly obtained under relatively slow cooling can occur.

This paper gives an overview of some of the recent developments in the area of chip calorimetry. Using several chip calorimeters developed at Xensor Integration and tested by users, examples of chip calorimetry and its applications will be given. Examples of chip calorimeters developed at various universities are given to widen the overview. The examples will be used to give more insight in the design and fabrication of various chip calorimeters.

AC chip calorimetry is used to study the phase separation behavior of 100 nm thin poly(vinyl methyl ether)/poly(styrene) (PVME/PS) blend films. Using the on-chip heaters, very short (10 ms–10 s) temperature jumps into the temperature window of phase separation are applied, simulating laser heating induced patterning. These temperature pulses produce a measurable shift in the glass transition temperature, evidencing phase separation. The effect of pulse length and height on phase separation can be studied. The thus phase separated PVME/PS thin films remix rapidly, in contrast with measurements in bulk. AC chip calorimetry seems to be a more sensitive technique than atomic force microscopy to detect the early stages of phase separation in polymer blend thin films.

Tammann’s two-stage crystal-nuclei-development method is applied for analysis of the thermal stability of homogenously formed crystal nuclei of poly(butylene isophthalate) (PBI) as well as their possible reorganization on transferring them to the growth temperature, using fast scanning chip calorimetry. Crystal nuclei were formed at 50 °C, that is, at a temperature only slightly higher than the glass transition temperature, and developed to crystals within a pre-defined time at the growth temperature of 85 °C. The number of nuclei, overcritical at the growth temperature, was detected as a function of the transfer-conditions (maximum temperature, heating rate) by evaluation of the developed crystal fraction. For different size-distributions of crystal nuclei, as controlled by the nucleation time, there is detected distinct reduction of the nuclei number on heating to maximum temperatures higher than about 90 to 110 °C, with the latter value holding for longer nucleation time. Longer nucleation allows for both increasing the absolute nuclei number and generation of an increased fraction of larger nuclei. Heating at 1000 K/s to 140–150 °C causes “melting” of even the most stable nuclei. While direct transfer of crystal nuclei from the nucleation temperature (50 °C) to the growth temperature (85 °C) reveals negligible effect of the transfer-heating rate, in-between heating to higher temperatures is connected with distinct nuclei-reorganization above 85 °C on heating slower than 1000–10.000 K/s. The performed study not only provides specific valuable information about the thermal characteristics of crystal nuclei of PBI but also highlights the importance of proper design of Tammann’s nuclei development experiment for analysis of nuclei numbers. With the evaluation of critical rates of temperature-change for suppression of non-isothermal formation of both nuclei and crystals, the kinetics of crystallization of the slow crystallizing PBI is further quantified.