Crystallization of selective polymorph using relationship between supersaturation and solubility

For polymorph screening, the plot of ΔC_met/C_c against C^*/C_c in nucleation kinetics was investigated. The polymorph screening for forms I and II and amorphous form of clopidogrel hydrogen sulfate was carried out according to the nucleation kinetics expressed by this plot. The stability order of polymorphs for famotidin was also predicted successfully by this model. This model was used in the expectation of supersaturation level for polymorphic formation. Two types of polymorphic crystallization: transformation from metastable form to stable form and nucleation and growth of polymorphic form without transformation can be explained. Amorphous form was also expected by this model. Even though polymorphs depend on lots of crystallization parameters such as solvent, temperature, concentration, cooling rate, and so forth, plot of ΔC_met/C_c and the C^*/C_c in various nucleation kinetics gives a guide line for screening of polymorph. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1372–1379, 2015     

Polymorphism of POS. II. kinetics of melt crystallization

Melt crystallization of four polymorphs of POS, α,δ, pseudo-β′ andβ, was examined with pure samples (>99.9%). Induction time, τ, for newly occurring crystals was measured with a polarizing microscope equipped with a temperature-controlled growth cell. Rate of crystallization, 1/τ, was obtained for each polymorph, whose identification was done with x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Two modes of crystallization, melt cooling and melt mediation, were applied. From these experiments, the following conclusions were obtained: (i) The rate of melt-mediated crystallization was always higher than of simple melt cooling; (ii) the pseudo-β′ form was crystallized in a wider range of temperature than the less stable δ form; (iii) the occurrence behavior of the polymorphs differed between simple melt cooling and melt mediation; (iv) the δ form was crystallized only by simple melt cooling in a narrow range of temperature, 25.5°C∼28.3°C. This means that there is a possibility that δ may result from racemic compounds that are crystallized in a specific manner. The experimental results are discussed in comparison to 1,3-dipalmitoyl2-oleoylglycerol (POP), 1,3-distearoyl-2-oleoylglycerol (SOS) and cocoa butter.     

New understanding for the formation of conductive network in the nanocomposites during the crystallization of matrix

Crystallization behavior of conductive composite has a great effect on the formation of conductive network. But very few studies have exposited, specially on the micro level, the evolution of conductive network during the crystallization of matrix. In this study, the conductive network was found to be destroyed by crystallization behavior of isotactic polypropylene (iPP) matrix, and the carbon black (CB) particles were rejected to the amorphous region or the inter-lamellar of spherulite. By comparison, the low-structure carbon black (LCB) filled system was more sensitive to the crystallization of matrix than the high-structure carbon black (HCB) filled system because of the morphology and interaction force of the CB primary aggregate. A secondary increase in volume resistivity during terminal crystallization was observed in iPP/LCB composite when it isothermally crystallized at a certain temperature. In that case, an analysis of crystallization kinetics of composites through a modified Lauritzen-Hoffman model indicated that the transition from regime I→II in the isothermal crystallization process of iPP matrix showed significant influence on the network formation of LCB particles.     

Effect of pressure on the melting and crystallization behaviour of isotactic polybutene-1

The formation, melting and phase transition of isotactic polybutene-1 under high hydrostatic pressures were studied by high-pressure d.t.a. and X-ray diffraction up to 5 kbar. The d.t.a. thermogram of melting of form I shows a single endothermic peak up to 5 kbar. Form II crystallized directly from the melt at atmospheric pressure is metastable and it transforms to form I by the application of pressure. Above 900 bar, it transforms to form I completely and the endothermic peak of melting of form II is not observed. On crystallization from the melt under high pressure, the percentage content of form I' increases with crystallization pressure and at 1.6 kbar only form I' is crystallized. Above 2 kbar form II', which shows the same X-ray diffraction pattern as form II, is crystallized from the melt. The percentage content of form II' increases with pressure above 2 kbar, and that of form I' decreases up to 5 kbar. Upon heating under high pressure above 2 kbar, a solid-solid transition from form II' to form I' is observed in d.t.a. traces and the transition is confirmed by high-pressure X-ray diffraction. The melting temperature is expressed in the form of a quadratic equation as a function of pressure for four different forms in IPB-1.     

Isothermal crystallization kinetics of refined palm oil

The induction times for the crystallization, under isothermal conditions, of refined, bleached, and deodorized palm oil from the melt were studied by viscometry. At temperatures below 295 K, the crystallization of palm oil was observed to occur in a two-stage process. This two-stage process was caused by the fractionation of palm oil, most probably into the stearin and olein fractions. At temperatures higher than 295 K, only a single-stage crystallization process was observed. As seen under polarized light microscopy, spherical crystals were initially formed from the first fraction at temperatures from 287 to 293 K. The diameters of these spherical crystals decreased as the temperature increased. After that, needle-shaped crystals were formed from the second fraction and continued to grow from the surface of these spherical crystals until the spherical crystals were fully enclosed, i.e., the cocrystallization of two polymorphs was observed. At temperatures higher than 293 K, the needle-shaped crystals formed from a mixture of the two fractions were found to be the only polymorphs developed with the onset of crystallization. X-ray diffraction results showed that for temperatures below 295 K, the spherical crystals formed from the first fraction were in α form, whereas the needle-like crystals that nucleated later from the second fraction were in β′ form. β′ crystals were the only polymorphs formed for temperatures above 295 K. The results obtained were in good agreement with the discontinuity observed in the induction time vs. temperature curve. Activation free energies for nucleation were calculated according to the Fisher-Turnbull equation for the various polymorphic forms. Viscometry was observed to be a sensitive method for characterizing the overall crystallization process. This technique is suitable for induction time studies of palm oil crystallization, especially at lower temperatures and with viscous oil.     

The effects of shear and temperature history on the crystallization of chocolate

Experiments have been carried out on the tempering of chocolate using a temperature-controlled shearing rig with a concentric cylinder geometry. This design maximizes uniformity of shear rate during tempering in contrast to most tempering devices where shear is often concentrated in a small part of the chocolate mass. Samples were subsequently cooled in a differential scanning calorimeter (DSC) to monitor how the sample crystallized, and then reheated to gain further information on the melting points of the polymorphs formed. The results can be interpreted using established theories on the crystallization mechanism. It was found that at least two polymorphic forms could be generated. The higher melting form predominated provided the shear rate was high enough, the temper time long enough, the rewarm temperature low enough, and the DSC scan rate slow enough. For parameters affecting the nucleation stage (temper time and shear rate), it was found that the transition was a sharp one, reflecting the notion that seed crystals need to grow past a threshold point in order to be stably formed. Raising the rewarm temperature had the effect of destroying seed nuclei, but this was a more gradual process. The bimodal nature observed of the melting points compared to the more spread-out behavior of crystallization temperatures reflects the kinetic constraints found in crystallization which are not found on melting.     

Polymorphism of D-mannitol: Crystal structure and the crystal growth mechanism

The polymorphism of D-Mannitol(mannitol) is reviewed in this paper. It was found that the structure of the stable form is consistent in most literatures, but different authors have given different information about the two metastable forms. Therefore the commonly used nomenclature of mannitol was summarized based on the crystal unit cell parameters with the help of X-ray powder diffraction. Moreover, the crystal growth mechanism of mannitol polymorphs was summarized. Considering the lack of kinetic data for the metastable form especially, a reported method was attempted to apply to δ mannitol in an aqueous cooling crystallization process based on the induction time previously measured, and it was identified that the growth of the δ form follows the two-dimensional(2D) nucleationmediated mechanism. The results also indicate that the method based on induction time and supersaturation should have the potential to be expanded to the metastable polymorphs for the growth property study in a bulk system.     

滑石粉对PB-1熔融、结晶行为的影响

采用双螺杆挤出机熔融制备了聚丁烯–1(PB-1)/滑石粉复合材料,研究了滑石粉含量对PB-1熔融及结晶行为的影响。结果表明,滑石粉显著促进了PB-1的结晶过程,其成核能力在滑石粉质量分数为1%时最佳。非等温结晶动力学研究表明,在滑石粉的实验用量范围内(1%～10%),要达到相同的结晶度,PB-1/滑石粉复合材料的完成温度明显高于纯PB-1的完成温度。当滑石粉质量分数为1%～5%时,要达到相同的结晶度,PB-1/滑石粉所需的时间明显比纯PB-1短;当用量为7%时稍短;当用量为10%时又稍长。但滑石粉不影响PB-1的依热成核方式和三维生长机制。偏光显微镜结果表明滑石粉对PB-1的异相成核作用显著。广角X射线衍射研究表明滑石粉阻碍了PB-1由晶型Ⅱ向晶型Ⅰ的转变过程,使晶型转变变缓。     

Multiple melting behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) investigated by differential scanning calorimetry and infrared spectroscopy

The multiple melting behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx = 12 mol%) isothermally crystallized from the melt state has been characterized by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The influence of different experimental variables (such as crystallization temperature, time, and heating rate) on the multiple melting behavior of P(HB-co-HHx) was investigated by using DSC. Moreover, it has been further examined by monitoring intensity changes of the characteristic IR bands during the subsequent heating process. For the isothermally crystallized P(HB-co-HHx) samples, triple melting peaks were observed upon heating. The weak lowest-temperature DSC endotherm I always appears at the position just above the crystallization temperature, and shifts to a higher temperature linearly with the logarithm of the crystallization time. The combination of DSC and IR results suggested that the occurrence of peak I was a result of the melting of crystals formed upon long-time annealing. As for the other two main melting endothermic peaks, endotherm II corresponds to the melting of crystals formed during the primary crystallization, and endotherm III is ascribed to the melting peak of the crystals formed by recrystallization during the heating process.     

Stability of form II of syndiotactic polypropylene confirmed by cold and melt crystallization in supercritical carbon dioxide

The form II of syndiotactic polypropylene (sPP) has been found more thermodynamically stable than form I when melt crystallized at pressures above 150 MPa, while the reverse occurs below 150 MPa. In the present study, through the cold and melt crystallization in supercritical CO₂ the stability of various polymorphic forms of sPP, especially form II, was confirmed by using Fourier-transform infrared spectroscopy and wide-angle X-ray diffraction. Compared with the formation of pure form I at high temperatures under ambient condition, a mixture of forms I and II was formed by both the cold and melt crystallization in supercritical CO₂. This atmosphere changed the relative stability of forms I and II, and made the form II more thermodynamically stable than form I. The increased solubility parameters of the surroundings, at which the form II was formed, also confirmed the stability of form II over form I in supercritical CO₂. The incubation pressure was the key factor affecting the formation and amount of form II. Supercritical CO₂ provides a combining severe condition to obtain the form II crystal, although its pressure was much lower than the elevated pressures (>150 MPa) reported before.     

Molecularly imprinted polymer based on multiwalled carbon nanotubes for ribavirin recognition

The polymorphic transformations (from form II to form I) of three kinds of isotactic poly(1-butene) were characterized by FTIR and by changes in their macroscopic physical and mechanical properties, including density and tensile characteristics. The kinetics of the form II to form I transformation were followed by performing FTIR measurements in real time. At 25?°C, as the crystallization time increased, the characteristic FTIR peak of form I of the poly(1-butene) increased, while that of form II diminished and finally disappeared. The polymorphic transformation from form II to form I of the poly(1-butene) obtained by the solution method (S-PB) occurred the most rapidly, followed by the corresponding transformation for the poly(1-butene) obtained from Mitsui Chemicals (M-PB) and then that for the poly(1-butene) produced using the high-pressure bulk polymerization method (B-PB). This transformation behavior is due to the higher isotacticity of the S-PB, as also demonstrated by the results of the density and tensile tests. The density of S-PB is higher than the densities of M-PB and B-PB due to its greater crystallinity.     

Crystallization behavior of low molecular mass isotactic poly(propylene) fractions

Summary The overall crystallization and linear crystal growth kinetics for the (monoclinic) -form of low molecular mass isotactic poly(propylene) (i-PP) fractions have been studied. Two processes can be found for the overall crystallization study via differential scanning calorimetry (DSC). Based on the nucleation theory, both the half-life time of the first process in overall crystallization kinetics and the linear crystal growth data show two regime transitions, namely, regime I/II and II/III transitions.     

Thermal degradation of poly(aryl-ether–ether-ketone) (PEEK): A differential scanning calorimetry study

Differential scanning calorimetry (DSC) has been used to study the crystallization kinetics and thermal characteristics of poly(aryl-ether–ether-ketone) (PEEK) samples heated under a variety of conditions. Samples were heated in nitrogen and air at temperatures between 380 and 420°C for times up to 120 min. The results indicate that as the holding time and temperature of the melt increased, the amount of recrystallizable material decreased, especially when heated in air. Isothermal crystallization kinetics confirmed the presence of a two-stage crystal nucleation and growth process with Avrami exponents of the order of about 2.4 and 1.5 for the first and second processes, respectively. Analysis of the primary crystallization process using the Avrami equation revealed that PEEK samples heated above the melt temperature in air crystallized at a much slower rate than samples heated in nitrogen.     

Isothermal crystallization of hydrogenated sunflower oil: I—Nucleation

Nucleation kinetics of sunflower seed oil, which was hydrogenated under two different conditions, was studied by means of a polarized light microscope and an optical setup with a laser as the light source. When the laser was used, observed induction times were shorter than the ones measured by the microscope. The laser method was found to be more sensitive and accurate. Two different crystallization behaviors were found depending on the chemical composition of the samples. Samples with high content of trielaidin crystallized in the β form at temperatures close to the melting points. They exhibited both β′ and β forms depending on crystallization temperature, as happens in natural semisolid fats such as palm oil. Samples with high content of mixed oleic and elaidic triacylglycerols crystallized in the β′ form even at temperatures close to the melting points and they did not show β form under the conditions used in this study. Activation free energies of nucleation for hydrogenated sunflower seed oil were low for the two hydrogenation conditions. It can be concluded that nucleation of sunflower seed oil is a fast process and initially needs low supercooling. These results are also important from a practical point of view for processing design, especially in regards to processes in which fats should be completely crystallized by the end of the production line.     

PA1212的结晶动力学研究

采用DSC方法研究了PA1212的非等温和等温结晶动力学。Avrami方程可以适用PA1212的等温结晶过程,其Avrami指数为2．51～2．87,等温结晶活化能为-131．9 kJ/mol;在非等温结晶过程中,结晶速率随降温速率的增大而提高,综合利用Avrami方程和Ozawa方程得到Avrami指数与Ozawa指数的比值为1．31～1．49,非等温结晶活化能为-87．96 kJ/mol。结果表明,与其他聚酰胺相比,PA1212较容易结晶。     

Melting and crystallization behavior of poly(trimethylene 2,6-naphthalate)

The melting and crystallization behavior of poly(trimethylene 2,6-naphthalate) (PTN) are investigated by using the conventional DSC, the temperature-modulated DSC (TMDSC), wide angle X-ray diffraction (WAXD) and polarized light microscopy. It is observed that PTN has two polymorphs (α- and β-form) depending upon the crystallization temperature. The α-form crystals develop at the crystallization temperature below 140 °C while β-form crystals develop above 160 °C. Both α- and β-form crystals coexist in the samples crystallized isothermally at the temperature between 140 and 160 °C. When complex multiple melting peaks of PTN are analyzed using the conventional DSC, TMDSC and WAXD, it is found that those arise from the combined mechanism of the existence of different crystal structures, the dual lamellar population, and melting-recrystallization-remelting. The equilibrium melting temperatures of PTN α- and β-form crystals determined by the Hoffman-Weeks method are 197 and 223 °C, respectively. When the spherulitic growth kinetics is analyzed using the Lauritzen-Hoffmann theory of secondary crystallization, the transition temperature of melt crystallization between regime II and III for the β-form crystals is observed at 178 °C. Another transition is observed at 154 °C, where the crystal transformation from α- to β-form occurs.     

Crystallization behavior and morphology of poly(ethylene 2,6-naphthalate)

The crystallization behavior and morphology of poly(ethylene 2,6-naphthalte) (PEN) were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and transmission electron microscopy (TEM). POM results revealed that PEN crystallized at 240 °C shows the coexistence of α and β-form spherulite morphology with different growth rates. In particular, when PEN crystallized at 250 °C, the morphology of spherulites showed a squeezed peanut shape. The Avrami exponents decreased from 3 to 2.8 above the crystallization temperature of 220 °C, indicating a decrease in growth dimension. Analysis from the secondary nucleation theory suggests that PEN crystallized at 240 °C has crystals with both regime I and regime II. In TEM observation, the ultra-thin PEN film crystallized at 200 °C showed the spherulitic texture with characteristic diffractions of α-form, while PEN crystallized at 240 °C generated an axialite structure with only β-form diffraction patterns. In addition, despite a long crystallization time of 24 h, amorphous regions were also observed in the same specimen. It was inferred that the initiation of PEN at 240 °C generates only β-form crystals from axialite structures.     

Crystallization of block copolymers in restricted cylindrical geometries

Using Tapping Mode atomic force microscopy, we studied crystallization of polymers in confined cylindrical geometries of micro-phase separated asymmetric diblock copolymers, deposited in thin films onto solid substrates. We observed that in most cases crystallization occurs separately and independently in each cylinder of the mesophase pattern. We followed the kinetics of the crystallization process with time and found an influence of the lateral size of the cylindrical morphology on the rate of crystallization. The present data are compared to previous results on spherical mesophase patterns. The growth rate within one single cylinder was found to be not necessarily constant. Depending on the amount of crystallized material and the molecular weight, structural relaxations of the crystals can have very strong influence on the amorphous matrix and can even lead to the destruction of the mesophase pattern, allowing for break-out crystallization. As a consequence of break-out crystallization, crystallization kinetics changed considerably since the crystal growth was not limited anymore to the confinement imposed by the cylinders.     

On the time for fold surfaces to order during the crystallization of polyethylene from the melt and its dependence on molecular parameters

New experiments underpin the interpretation of the basic division in crystallization behaviour of polyethylene in terms of whether or not there is time for the fold surface to order before the next molecular layer is added at the growth front. For typical growth rates, in Régime II, polyethylene lamellae form with disordered {001} fold surfaces then transform, with lamellar thickening and twisting, towards the more-ordered condition found for slower crystallization in Régime I, in which lamellae form with and retain {201} fold surfaces. Several linear and linear-low-density polyethylenes have been used to show that, for the same polymer crystallized alone or in a blend, the growth rate at which the change in initial lamellar condition occurs is reasonably constant thereby supporting the concept of a specific time for surfaces to attain the ordered {201} state. This specific time, in the range from milliseconds to seconds, increases with molecular length, and in linear-low-density polymer, for higher branch contents.     

Local conformation controlled crystallization of isotactic poly(butene-1)

The slow spontaneous solid-solid transition from metastable form II to stable form I in typical isotactic polybutene-1 (iPB-1) homopolymer after melt crystallization may be unavoidable and it is challenging to obtain form I directly from bulk iPB-1 melt. In this work, by DSC and WAXS, form I was observed to directly crystallize from bulk iPB-1 while cooling to T far below the crystallization temperature T_c of form II. It is further proposed that the local formation of 3/1 helix conformation is the determining process of direct formation of form I and there exists a temperature window for 3/1 helix conformation to form at low T due to the competition between the entropy effect and the synergistic effect of enthalpy and the energy barrier. The key of polymorph selection of iPB-1 lies in the T-dependent formation of the crystal-favored helix conformations. The results could shed lights on developing charming industrial approaches to obtain the stable form I directly in bulk iPB-1 as well as on understandings to the physics behind polymer crystallization and polymorph selection processes.