Crystallization of Random Metallocene-Catalyzed Propylene-Based Copolymers with Ethylene and 1-Hexene on Rapid Cooling

Propylene-based random copolymers with either ethylene or 1-hexene as comonomer, produced using a metallocene catalyst, were studied regarding their crystallization behaviors, with a focus on rapid cooling. To get an impression of processing effects, fast scanning chip calorimetry (FSC) was used in addition to the characterization of the mechanical performance. When comparing the comonomer type and the relation to commercial grades based on Ziegler–Natta-type catalysts, both an interaction with the catalyst-related regio-defects and a significant difference between ethylene and 1-hexene was observed. A soluble-type nucleating agent was found to modify the behavior, but to an increasingly lesser degree at high cooling rates.

Surface Crystal Nucleation and Growth in Poly (ε-caprolactone): Atomic Force Microscopy Combined with Fast Scanning Chip Calorimetry

By using an atomic force microscope (AFM) coupled to a fast scanning chip calorimeter (FSC), AFM-tip induced crystal nucleation/crystallization in poly (ε-caprolactone) (PCL) has been studied at low melt-supercooling, that is, at a temperature typically not assessable for melt-crystallization studies. Nanogram-sized PCL was placed on the active/heatable area of the FSC chip, melted, and then rapidly cooled to 330 K, which is 13 K below the equilibrium melting temperature. Subsequent isothermal crystallization at this temperature was initiated by a soft-tapping AFM-tip nucleation event. Crystallization starting at such surface nucleus led to formation of a single spherulite within the FSC sample, as concluded from the radial symmetry of the observed morphology. The observed growth rate in the sub-micron thin FSC sample, nucleated at its surface, was found being much higher than in the case of bulk crystallization, emphasizing a different growth mechanism. Moreover, distinct banding/ring-like structures are observed, with the band period being less than 1 µm. After crystallization, the sample was melted for gaining information about the achieved crystallinity and the temperature range of melting, both being similar compared to much slower bulk crystallization at the same temperature but for a much longer time.

Extending Cooling Rate Performance of Fast Scanning Chip Calorimetry by Liquid Droplet Cooling

The liquid droplet cooling technique for fast scanning chip calorimetry (FSC) is introduced, increasing the cooling rate for large samples on a given sensor. Reaching higher cooling rates and using a gas as the cooling medium, the common standard for ultra-fast temperature control in cooling requires reducing the lateral dimensions of the sample and sensor. The maximum cooling rate is limited by the heat capacity of the sample and the heat exchange between the gas and the sample. The enhanced cooling performance of the new liquid droplet cooling technique is demonstrated for both metals and polymers, on examples of solidification of large samples of indium, high-density polyethylene (HDPE) and poly (butylene 2,6-naphthalate) (PBN). It was found that the maximum cooling rate can be increased up to 5 MK/s in room temperature environment, that is, by two orders of magnitude, compared to standard gas cooling. Furthermore, modifying the droplet size and using coolants at different temperatures provide options to adjust the cooling rate in the temperature ranges of interest.

Fast-Scanning Chip-Calorimetry Measurement of Crystallization Kinetics of Poly(Glycolic Acid)

We report fast-scanning chip-calorimetry measurement of isothermal crystallization kinetics of poly(glycolic acid) (PGA) in a broad temperature range. We observed that PGA crystallization could be suppressed by cooling rates beyond -100 K s−1 and, after fast cooling, by heating rates beyond 50 K s-1. In addition, the parabolic curve of crystallization half-time versus crystallization temperature shows that PGA crystallizes the fastest at 130 °C with the minimum crystallization half-time of 4.28 s. We compared our results to those of poly(L-lactic acid) (PLLA) with nearby molecular weights previously reported by Androsch et al. We found that PGA crystallizes generally more quickly than PLLA. In comparison to PLLA, PGA has a much smaller hydrogen side group than the methyl side group in PLLA; therefore, crystal nucleation is favored by the higher molecular mobility of PGA in the low temperature region as well as by the denser molecular packing of PGA in the high temperature region, and the two factors together decide the higher crystallization rates of PGA in the whole temperature range.

Extending Cooling Rate Performance of Fast Scanning Chip Calorimetry by Liquid Droplet Cooling

The liquid droplet cooling technique for fast scanning chip calorimetry (FSC) is introduced, increasing the cooling rate for large samples on a given sensor. Reaching higher cooling rates and using a gas as the cooling medium, the common standard for ultra-fast temperature control in cooling, requires reducing the lateral dimensions of the sample and sensor. The maximum cooling rate is limited by the heat capacity of the sample and the heat exchange between the gas and the sample. The enhanced cooling performance of the new liquid droplet cooling technique is demonstrated for both metals and polymers, on examples of solidification of large samples of indium, high-density polyethylene (HDPE), and poly (butylene 2,6-naphthalate) (PBN). It was found that the maximum cooling rate can be increased up to 5 MK/s in room temperature environment, that is, by 2 orders of magnitude, compared to standard gas cooling. Furthermore, modifying the droplet size and using coolants at different temperatures provide options to adjust the cooling rate in the temperature ranges of interest.

New Insights into Crystallization of Heterophasic Isotactic Polypropylene by Fast Scanning Chip Calorimetry

The crystallization kinetics of metallocene-catalyzed heterophasic isotactic polypropylene composed of a matrix of isotactic polypropylene (iPP) and rubbery particles made of random ethylene–propylene copolymers (EPC), often denoted as heterophasic iPP copolymers, was analyzed as a function of the cooling rate and supercooling in nonisothermal and isothermal crystallization experiments, respectively. Fast scanning chip calorimetry (FSC) allowed assessing crystallization at processing-relevant conditions, and variation of the content (0–39 wt %) and composition (0–35 wt % propylene counits) of the EPC particles revealed qualitatively new insight about mechanisms of heterogeneous crystal nucleation. For neat iPP homopolymer, the characteristic bimodal temperature dependence of the crystallization rate due to predominance of heterogeneous and homogeneous crystal nucleation at high and low temperatures, respectively, is reconfirmed. At high temperatures, in heterophasic iPP, the here studied ethylene-(C2)-rich EPC particles accelerate crystallization of the iPP-matrix, with the acceleration or nucleation efficacy correlating with the EPC-particle content. The crystallization time reduces by more than half in presence of 39 wt % EPC particles. An additional nucleating effect of the EPC particles on iPP-matrix crystallization is detected after their crystallization, suggesting that liquid/rubbery particles are less effective than solid/semicrystalline particles in affecting crystallization of the surrounding iPP-matrix. At low temperature, homogeneous crystal nucleation in the iPP-matrix outpaces all heterogeneous nucleation effects, and the matrix-crystallization rate is independent of the sample composition. The obtained results lead to the conclusion that the crystallization kinetics of iPP can be affected significantly by the content and composition of EPC particles, even towards superfast crystallizing iPP grades.

Assessment of Crystallinity Development during Fused Filament Fabrication through Fast Scanning Chip Calorimetry

Although semi-crystalline polymers are associated with considerably better mechanical properties and thermal stability compared to their amorphous counterparts, using them as feedstock for Fused Filament Fabrication still poses some major challenges. Hence, the development of printed part crystallinity during printing should be fully understood in order to control the developed weld strength, as well as part shrinkage and warpage. Infrared thermography was utilized to record the thermal history of deposited layers while printing a single-layer wall geometry, employing two PA 6/66 copolymers with distinct molecular weights as feedstock. Print settings were varied to establish which settings are essential to effectively monitor final part crystallinity. The resulting temperature profiles were simulated in a Fast Scanning Chip Calorimetry device that allows for the rapid heating and cooling rates experienced by the printed polymer. Both liquefier temperature and print speed were found to have very little influence on the total attained crystallinity. It became apparent that the build plate, set at a temperature above the polymer’s glass transition temperature, imposes a considerable annealing effect on the printed part. A reduced molecular weight was observed to enhance crystallinity even more strongly. The presented methodology proves that Fast Scanning Chip Calorimetry is an effective tool to assess the impact of both print parameters and feedstock characteristics on the crystallization behavior of semi-crystalline polymers over the course of printing.