Continuous cooling and isothermal crystallization of polycaprolactone

In this article we present overall crystallization characteristics of five polycaprolactone samples with mean molecular weights ranging from 50,000 to 400,000. The crystallization temperatures and heats of crystallization are determined as a function of mean molecular weight as well as for cooling rates in the range 0.31 to 40 K/min. Our results show a decrease in crystallization temperature from 320 to 300 K at increasing molecular weight and cooling rate. The heat of crystallization shows a slight decrease within the cooling rate interval and a decrease from about 68 to 48 J/g with increasing molecular weight. We analyze the continuous cooling data according to the Ozawa model for nonisothermal crystallization and compare them with our isothermal data analyzed with the Avrami model. Both the Ozawa and Avrami models give exponent parameters in the range 2.9 to 3.6. In the investigated temperature range and for all samples, we find a nucleation controlled crystallization. At the lowest temperatures, the Ozawa analysis indicates an increasing dependency on limitations in chain mobility. The higher molecular species have in general a slower crystallization rate, with half crystallization times increasing with a factor of about five within the molecular weight range at 320 K. © 1996 John Wiley & Sons, Inc.     

Effect of molecular weight on crystallization and melting of poly(trimethylene terephthalate). 1: Isothermal and dynamic crystallization

The crystallization behavior of poly(trimethylene terephthalate) as a function of molecular weight was investigated under isothermal and dynamic cooling conditions using a differential scanning calorimeter (DSC) and polarized light optical microscopy (POM). THe overall rate of bulk crystallization increased with molecular weight. An Avrami analysis of the isothermal crystallization kinetics indicated that the crystallization rate constant increased with increasing molecular weight. The Avrami exponent, n, approached 2 and was nearly independent of both molecular weight and temperature. The modified Avrami analysis developed by Jeziorny and Ozawa was applied to the dynamic crystallization data. At the same cooling rate, higher molecular weight resulted in a narrower crystallization peak, higher onset crystallization temperature, and larger rate constant (Z_t)^1/n. Higher molecular weight resulted in larger cooling function of dynamic crystallization K(T) and lower Ozawa exponent m. For dynamic crystallization, the average value of the Avrami exponent varied from 3.4 to 3.8 and the average value of the Ozawa exponent changed from 2.3 to 2.6 as the number‐average molecular weight changed from 13,000 to 67,000. Morphology studies indicated that both the isothermal crystallization and the dynamic crystallization of PTT from the melt were thermal nucleation processes, and for a fixed temperature between 190°C and 210°C, the nucleation density increased with increasing the molecular weight.     

Kinetics of isothermal and non‐isothermal crystallization of poly(butylene terephthalate)/ liquid crystalline polymer blends

The melting behavior and isothermal and non‐isothermal crystallization kinetics of poly(butylene terephthalate) (PBT)/thermotropic liquid crystalline polymer (LCP), Vectra A950 (VA) blends were studied by using differential scanning calorimetry. Isothermal crystallization experiments were performed at crystallization temperatures (T_c), of 190, 195, 200 and 205°C from the melt (300°C) and analyzed based on the Avrami equation. The values of the Avrami exponent indicate that the PBT crystallization process in PBT/VA blends is governed by three‐dimensional morphology growth preceded by heterogeneous nucleation. The overall crystallization rate of PBT in the melt blends is enhanced by the presence of VA. However, the degree of PBT crystallinily remains almost the same. The analysis of the melting behavior of these blends indicates that the stability and the reorganization process of PBT crystals in blends are dependent on the blend compositions and the thermal history. The fold surface interfacial energy of PBT in blends is more modified than in pure PBT. Analysis of the crystallization data shows that crystallization occurs in Regime II across the temperature range 190°C‐205°C. A kinetic treatment based on the combination of Avrami and Ozawa equations, known as Liu's approach, describes the non‐isothermal crystallization. It is observed that at a given cooling rate the VA blending increases the overall crystallization rate of PBT.     

Effects of fibers on the crystallization of poly(phenylene sulfide)

The isothermal crystallization of unreinforced poly(phenylene sulfide) (PPS) and PPS filled with glass, carbon, and aramid fibers was studied by differential scanning calorimetry. The Avrami exponent and rate constant are reported, but the crystallization half-times were used to compare the effects of different fibers on the rate of PPS crystallization. The aramid and carbon fibers decreased the crystallization half-time with the aramid fiber having the most pronounced effect. The glass fibers affected the crystallization half-time only at the higher crystallization temperatures. The aramid filled PPS exhibited anomalous degree of crystallinity behavior in that the degree of crystallinity passed through a minimum as a function of temperature. The other systems all exhibited increasing degree of crystallinity with increasing crystallization temperature. Finally, the Avrami plot for the aramid filled PPS is not linear, and the data are fitted better with two linear regions indicating that two types of crystallization processes may be present.     

Melting behavior,crystallization kinetics and morphology of random copolyesters of poly(2‐hydroxyethoxybenzoate) with ε‐caprolactone

The melting behavior after isothermal crystallization and the crystallization kinetics of random poly(2‐hydroxyethoxybenzoate/ε‐caprolactone) copolymers rich in 2hydroxyethoxybenzoate units were investigated by means of differential scanning calorimetry and hot‐stage optical microscopy. The observed multiple endotherms, which are commonly displayed by polyesters, were found to be influenced both by crystallization temperature and composition. By applying the Hoffman‐Weeks method to the melting temperatures of isothermally crystallized samples, the equilibrium melting temperatures of the copolymers were obtained. Furthermore, isothemal crystallization kinetics was analyzed according to the Avrami treatment. Values of the exponent n close to 3 were obtained, independently of crystallization temperature and composition, in agreement with a crystallization process originating from predeterminated nuclei and characterized by three‐dimensional spherulitic growth. Space‐filling banded spherulites were observed by hot‐stage optical polarizing microscopy at all the crystallization temperatures explored, the band spacing being affected by both crystallization temperature and composition. As expected, the introduction of ε‐caprolactone comonomeric units in the polymer chain of PHEBA was found to decrease its crystallization rate.     

Crystallization of poly(ε-caprolactone)

The isothermal crystallization behaviour of poly(ε-caprolactone), PCL, has been investigated by dilatometry and optical microscopy. Nucleation rates and spherulitic growth rates have been measured. At all temperatures tested a change in nucleation rate was observed early during the crystallization. Growth rates were linear over the whole of the crystallization range. The experimental results were analysed using the Avrami equation in which the experimentally observed time dependence of nucleation is used. The equation contains integer values of the Avrami exponent and describes adequately the crystallization behaviour of PCL. The difference between the apparent and true nucleation rates is emphasized, and difficulties in the calculation of rate constants are discussed.     

聚丙烯/超支化聚酯酰胺共混物的等温结晶动力学

将超支化聚酯酰胺(HBPEA)与聚丙烯(PP)挤出共混,得到PP/HBPEA共混物。利用差示扫描量热法研究了HBPEA改性PP的结晶行为和等温结晶动力学。结果表明:Avrami方程适用于研究PP/HBPEA共混物的等温结晶动力学,Avrami指数为1.48~2.11,晶体的生长方式为二维盘状方式。加入HBPEA可加快PP的结晶速率,在不同等温结晶温度条件下,HBPEA为0.4 phr时可使半结晶速率提高到纯PP的1.3~2.0倍。使用Hoffmann-Lauritizen理论计算了端表面自由能,发现加入HBPEA可降低垂直于分子链方向的界面自由能,促进PP链折叠,提高PP的结晶能力。     

Crystallization kinetics of polyethylene terephthalate. I. Isothermal crystallization from the melt

The crystallization behavior of polyethylene terephthalate (PET) was investigated as a function of molecular weight, temperature of crystallization, and polycondensation catalyst system. A detailed analysis of the crystallization course has been made utilizing the Avrami expression. The crystallization rate constants and the Avrami exponents were calculated. The results show that the rate constant and the mechanism of crystallization are dependent on the molecular weight, temperature, and the polycondensation catalyst system. The catalyst system often exhibits a more significant influence than the molecular weight in controlling the rate of crystallization of PET.     

Effect of molecular weight on the crystallization kinetics of poly(hexamethylene oxide)

Dilatometric crystallization isotherms have been analysed for poly(hexamethylene oxide) fractions ranging in molecular weight from 2200 to 33 500. Previously, the influence of the temperature and the time of melting in the reproducibility of the isotherms were studied. Deviations from the Avrami or Göler-Sachs free growth formulations are systematic with molecular weight and become more pronounced as the molecular weight increases. The Avrami exponent is an integral number, 4, and is independent of temperature and molecular weight. The crystallization rate goes through a maximum as a function of molecular weight and the location of this maximum depends on the undercooling. The crystallization temperature coefficient was studied using the three dimensional nucleation theory and it was found that the crystallization is described by a unique function of the free energy for nucleation when the change of the interfacial free energy with molecular weight is considered.     

Crystallization of polyformals: 1. Crystallization kinetics of poly(1,3-dioxolane)

Poly(1,3-dioxolane) fractions ranging in molecular weight from 8800 to 120 000 have been isothemally crystallized in the temperature range 25–41°C. From the dilatometric isotherms, the Avrami exponent is an integral number, 3, and is independent of temperature and molecular weight. The level of crystallinity is dependent on molecular weight and there is a change from ～55% for the highest molecular weight fraction to ～80% for the lowest molecular weight fraction. The overall crystallization rate temperature coefficient was studied using two dimensional nucleation theory and it was found that the interfacial free energies do not change with molecular weight. However, the usual plots are nonlinear in the whole range of crystallization temperatures. For the high crystallization temperatures the slope is about twice the low crystallization temperature slope, this change being related to a morphological transition.     

Nonisothermal melt crystallization kinetics of poly(ethylene terephthalate)/Barite nanocomposites

Poly(ethylene terephthalate) (PET)/Barite nanocomposites were prepared by direct melt compounding. The nonisothermal melt crystallization kinetics of pure PET and PET/Barite nanocomposites, containing unmodified Barite and surface‐modified Barite (SABarite), was investigated by differential scanning calorimetry (DSC) under different cooling rates. With the addition of barite nanoparticles, the crystallization peak became wider and shifted to higher temperature and the crystallization rate increased. Several analysis methods were used to describe the nonisothermal crystallization behavior of pure PET and its nanocomposites. The Jeziorny modification of the Avrami analysis was only valid for describing the early stage of crystallization but was not able to describe the later stage of PET crystallization. Also, the Ozawa method failed to describe the nonisothermal crystallization behavior of PET. A combined Avrami and Ozawa equation, developed by Liu, was used to more accurately model the nonisothermal crystallization kinetics of PET. The crystallization activation energies calculated by Kissinger, Takhor, and Augis‐Bennett models were comparable. The results reveal that the different interfacial interactions between matrix and nanoparticles are responsible for the disparate effect on the crystallization ability of PET. POLYM. COMPOS., 31:1504–1514, 2010. © 2009 Society of Plastics Engineers     

Crystallization of poly(ethylene terephthalate)/polycarbonate blends. I. Unreinforced systems

The crystallization and transition temperatures of poly(ethylene terephthalate) (PET) in blends with polycarbonate (PC) is considered using thermal analysis. Additives typically used in commercial polyester blends, transesterification inhibitor and antioxidant, are found to enhance the crystallization rate of PET. Differential scanning calorimetry (DSC) reveals two glass transition temperatures in PET/PC blends, consistent with an immiscible blend. Optical microscopy observations are also consistent with an immiscible blend. Small shifts observed in the T_g of each component may be due to interactions between the phases. The degree of crystallinity of PET in PET/PC blends is significantly depressed for high PC contents. Also, in blends with PC content greater than 60 wt %, two distinct crystallization exotherms are observed in dynamic crystallization from the melt. The isothermal crystallization kinetics of PET, PET modified with blend additives, and PET in PET/PC blends have been evaluated using DSC and the data analyzed using the Avrami model. The crystallization of PET in these systems is found to deviate from the Avrami prediction in the later stages of crystallization. Isothermal crystallization data are found to superimpose when plotted as a function of time divided by crystallization half-time. A weighted series Avrami model is found to describe the crystallization of PET and PET/PC blends during all stages of crystallization. © 1996 John Wiley & Sons, Inc.     

Kinetics of Isothermal Crystallization of Hydrogenated Castor Oil-in-Water Emulsions

Kinetics of isothermal crystallization of hydrogenated castor oil in water emulsions exhibiting multiple crystal morphologies have been studied experimentally by DSC and polarized light microscopy. The induction time of nucleation increases with the increase of the isothermal temperature under which crystallization occurred. Crystal growth has been observed by microscopy showing that both crystal morphologies, fibers and rosettes, grow linearly at the initial stage of crystallization and then slow down to reach a plateau value. The Avrami model, which has been widely used in kinetics studies of triacylglycerol systems, was employed to fit experimental results at different isothermal temperatures. It was found that experimental trends could be captured by introducing the volume fraction of each type of morphology into three-dimensional and one-dimensional full Avrami models.     

动态硫化EPDM/PP热塑性弹性体等温结晶行为研究

采用差示扫描量热仪（DSC）对比研究了聚丙烯（PP）和动态硫化三元乙丙橡胶/聚丙烯热塑性弹性体（EPDM/PPTPV）的等温结晶行为,并用Avrami方程对其进行等温结晶动力学分析。结果表明,在相同的结晶温度下,EPDM/PPTPV比PP结晶更快。2种试样的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV的Avrami指数n比PP的低,半结晶时间t_1/2比PP的低,结晶速率常数k比PP的高。     

Fast isothermal calorimetry of modified polypropylene clay nanocomposites

Calorimetric experiments at cooling rates comparable to those during injection molding, as an example, are needed to study phase transitions under conditions relevant for processing. Ultra fast scanning calorimetry is a technique which provides a means to analyze the materials of interest under rapid cooling conditions and it is a promising technique by which the crystallization behavior of composite systems based on fast crystallizing polymers like isotactic polypropylene (iPP) can be studied. By combining conventional DSC and ultra fast chip calorimetry isothermal crystallization experiments were performed in the whole temperature range between glass transition and melting temperature of iPP. Because of the very small time constant of the calorimeter, isothermal crystallization processes with peak times down to 100 ms were investigated after cooling the sample from the melt at 2000 K/s. iPP grafted with maleic anhydride (PPgMA) - montmorillonite clay nanocomposites were studied. The influence of various clay loadings on the crystallization behavior of PPgMA at different temperatures was followed by ultra fast isothermal calorimetry. PPgMA clay nanocomposites showed a variation in crystallization peak times with different clay loadings at crystallization temperatures between 70 °C and 100 °C. No influence of clay loading was observed at lower crystallization temperatures. At these temperatures, where the mesophase is formed and homogeneous nucleation is expected, the contribution of the clay as a nucleating agent is negligible. For crystallization at about 80 °C, where the α-phase is formed, the nucleating effect of the clay is observed yielding complex crystallization kinetics. In the temperature range 75-85 °C in some nanocomposites a double peak during isothermal crystallization was observed corresponding to a fast and a slow crystallization processes occurring simultaneously. At higher temperatures, above 120 °C, the clay slightly retards the crystallization process.     

原位增容PA6/PE-HD共混物的等温结晶动力学研究

采用差示扫描量热仪研究了原位增容聚酰胺6/高密度聚乙烯（PA6/PE-HD）共混物的等温结晶行为,采用Avrami方程分析了纯PA6和PA6/PE-HD共混物的等温结晶动力学,并通过Hoffman-Weeks方法计算出了共混物的平衡熔点。结果表明,二者的Avrami指数介于2.19~3.70之间,表明PA6晶体的生长方式为二维盘状生长和三维球晶生长并存,PE-HD的加入并没有影响PA6晶体的生长方式。偏光显微镜分析表明,纯PA6能够生成球晶,但加入PE-HD后,球晶尺寸明显变小,说明PE-HD的加入起到了异相成核的作用,加快了PA6的结晶过程。     

Effect of styrene-co-acrylonitrile on cold crystallization and mechanical properties of poly(ethylene terephthalate)

Blends of poly(ethylene terephthalate) (PET) with small amounts of styrene-co-acrylonitrile (SAN) were prepared by melt blending, and cold crystallization of these mixtures was investigated by means of differential scanning calorimetry. The results suggest that SAN interacts with the amorphous phase of PET, as observed by variations in the glass transition temperature and in the morphology of the blends, analyzed by scanning electron microscopy. The addition of 1% SAN promoted a significant reduction in the crystallization rate of PET, in a manner similar to that of an antinucleating agent. However, the crystallinity of the PET/SAN blends was comparable with that of neat PET; hence, mechanical properties were only slightly affected. Kinetic parameters were determined using Avrami theory; Avrami plots presented a nonlinear behavior at the end of crystallization, indicating that cold crystallization proceeds in two stages. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melting and crystallization behavior of aliphatic polyketones

The basic crystallization and melting behavior of three aliphatic polyketones were studied using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and optical microscopy. One resin was a perfectly alternating copolymer of ethylene and carbon monoxide, while the other two resins were terpolymers in which 6 mol % propylene was substituted for ethylene. Small decreases in the melting point and percent crystallinity of these materials were displayed with repeated melting. This behavior was attributed to light crosslinking as a result of condensation reactions occurring at temperatures in the melting range. WAXS showed that, after cooling to room temperature, the crystalline form in the copolymer was the α‐phase, while that in the terpolymers was the β‐phase. Optical microscopy revealed that the materials produce both negative and mixed birefringence spherulites under the conditions studied. SAXS measurements showed that the lamella thickness was largely a function of the temperature of crystallization. Attempts were made to measure the equilibrium melting temperature of these resins using several available techniques. The best value of the equilibrium melting temperature was concluded to be 278 ± 2°C for the copolymer. The results varied over a wide range for the terpolymers, but it is suggested that appropriate values are of order 252°C for the terpolymers. Crystallization kinetics studies, carried out under isothermal conditions using DSC, were evaluated using the Avrami equation. Results showed the Avrami exponent to lie in the range of 2–3. Spherulite growth rates were interpreted in terms of the secondary nucleation theory of Lauritzen and Hoffman. A transition from regime II to regime III was discovered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2124–2142, 2002     

Crystallization processes in poly(ethylene terephthalate) as modified by polymer additives and fiber reinforcement

The effect of fiber reinforcement on the crystallization kinetics of poly(ethylene terephthalate), or PET, was investigated using differential scanning calorimetry. The objective of the study was to determine how the effects of fiber reinforcement on PET crystallization are modified by the presence of polymer nucleating and plasticizing additives. Undirectional fiber composites were prepared using aramid and glass fibers in PET. The rate of crystallization of PET, as reflected by crystallization half-time, is seen to depend on reinforcing fiber type, crystallization temperature, and presence of nucleant or plasticizer. Howerver, degree of crystallinity of PET is largely unaffected by the presence of additives and reinforcing fibers. Crystallization kinetics are analyzed using the Avrami model for PET volume crystallized as a function of time. Avrami plots for PET and fiber-reinforced PET exhibit two linear regions, possibly corresponding to primary and secondary crystallization. The crystalline morphology of fiber-reinforced PET was also studied using polarized light microscopy. Results concerning nucleation density and growth morphology are used in explaining differences seen in crystallization kinetics in fiber-reinforced systems. © 1994 John Wiley & Sons, Inc.     

聚酯固相缩聚等温结晶特性的研究

聚酯(PET)固相缩聚(SSP)中切片的结晶性能及其演变影响固相缩聚反应,采用差示扫描量热仪(DSC)和热台偏光显微镜研究了固相缩聚反应前后PET切片的等温结晶特性。结果表明:PET切片在DSC中的等温结晶符合Avrami 方程,等温结晶温度升高,结晶速率常数K值减小,即结晶速率降低;热台偏光显微镜中不同等温结晶温度下形成了不同的球晶形态:黑十字消光图以及环形消光图;随着PET特性粘数(平均分子质量)增大,结晶速率常数K值减小,球晶生长速率减小,Avrami指数n值增大,形成更加复杂的消光图。对于固相缩聚前PET基础切片,球晶最大结晶速率在190℃左右。