Crystallization of poly(tetramethylene succinate) in blends with poly(ϵ‐caprolactone) and poly(ethylene terephthalate)

The crystallization behavior of polymer blends of poly(tetramethylene succinate) (PTMS) with poly(?‐caprolactone) (PCL) or poly(ethylene terephthalate) (PET) was investigated with differential scanning calorimetry under isothermal and nonisothermal conditions. The blends were prepared by solution casting and precipitation, respectively. The constituent polymers were semicrystalline materials and crystallized nearly independently in the blends. The addition of the second component to PTMS showed that PCL did not significantly influence the crystallinity of the constituents in the blends under isothermal conditions, whereas the crystallization of PTMS was slightly suppressed by crystalline PET. Nonisothermal crystallization under constant cooling rates was examined in terms of a quasi‐isothermal Avrami approach. In blends, the rates of crystallization were differently influenced by the second component. The rate of the constituent that crystallized at the higher temperature was barely influenced by the second component being in the molten state, whereas the rate of the second component, crystallizing when the first component was already crystalline, was altered differently under isothermal and nonisothermal conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 149–160, 2004     

Thermal and crystallization behavior of alloys of polyphenylene sulfide and high-density polyethylene

The thermal and crystallization behavior of alloys of two semicrystalline thermoplastics, namely, polyphenylene sulfide (PPS) and high-density polyethylene (HDPE) were studied by differential scanning calorimetry (DSC). The presence of a second component in the alloy was found to influence the nonisothermal crystallization process of both the component polymers. The crystallization temperature of PPS in the DSC cooling scan is significantly affected, whereas there is little variation in case of HDPE in the composition range studied. The morphological changes observed in both PPS and HDPE are similar. These include larger crystallite size, a narrower crystallite size distribution, and a lower degree of crystallinity in the alloys as compared to the homopolymers. The isothermal crystallization of the component polymers in the alloys is significantly different from that of the homopolymer. The composition dependence of the overall rate of isothermal crystallization is explained in terms of the competing processes of nucleation and crystal growth. The results show that blending of a high melting polymer with a low melting polymer accelerates the crystallization of the high melting polymer, even at low levels of about 10% of the lower melting component.     

Comparative study on quiescent crystallization kinetics of isotactic polyolefins

Quiescent melt crystallization rates of various polyolefins including high density polyethylene (PE), isotactic form of polypropylene (PP), polybutene‐1 (PB1), and poly(4‐methyl pentene‐1) (P4MP1) were investigated under both isothermal and nonisothermal conditions using differential scanning calorimetry (DSC). The order of overall crystallization rates under quiescent conditions from fast to slow was found to be: PE, P4MP1, PP and PB1. The Avrami equation was used to analyze isothermal and nonisothermal crystallization processes, respectively. In order to compare relative crystallization rates of these polymers, continuous cooling transformation curves for each polymer under nonisothermal condition as well as the plot of crystallization half‐time as a function of crystallization temperature under isothermal conditions were constructed. Comparisons were made of the relative rate of crystallization of the different isotactic polyolefins with each other and with reports in the literature. Isotactic polyolefins with linear side groups crystallize increasingly more slowly as the side group lengthens with polypentene‐1 (PPT1) and polyhexene‐1 (PH1) crystallizing even more slowly than PB1. It is notable that P4MP1, which has isobutyl as a bulky side group, and apparently poly(3‐methyl butene‐1) (P3MB1) showed fairly high crystallization rates. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crystallization kinetics of thermoplastic elastomeric blends based on ground tyre rubber

This work analyzes the crystallization process of thermoplastic elastomeric blends (TPE) based on ground tyre rubber (GTR). More specifically it analyzes the effect of GTR and fresh rubber materials, like ethylene propylene diene monomer (EPDM) and ethylene propylene rubber (EPR), on the crystallization of binary and ternary polypropylene (PP)‐based blends. The crystallization kinetics is studied under isothermal and nonisothermal conditions using differential scanning calorimetry (DSC). The kinetic parameters derived from the Avrami model are used to study the effect of temperature and rubber materials on the nucleation mechanism, the morphology of the crystalline structures, and the crystallization rate. Results reveal that GTR has a strong nucleating effect on PP and that its presence leads to higher crystallization rates. The EPDM presence has a slight effect on the PP crystallization process whereas EPR has no significant effect. From the DSC curves it is possible to detect an inverse relationship between temperature and the crystallization rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42589.     

Kinetic crystallization of polypropylene in ternary composites based on fiber‐reinforced PP‐EPDM blends

The crystallization of isotactic polypropylene (iPP) in its blends with ethylene–propylene–diene terpolymer (EPDM), reinforced with different fibers, is described in this work. In particular, the effects of both the fibers and the EPDM on the crystallization kinetics and morphology of iPP are analyzed. The study was performed using differential scanning calorimetry (DSC) in dynamic and isothermal conditions and optical microscopy. It was found that all the fibers act as effective nucleant agents on iPP crystallization independently of the blend composition. The results obtained highlight the accelerating effect of the fibers and of the EPDM on the PP crystallization up to a certain EPDM percentage. The halftime of crystallization, τ_1/2, and the overall crystallization rate, K_n, increase in the presence of all the fibers analyzed, showed the aramidic ones the most effective. The isothermal crystallization kinetics of ternary composites based on PP–EPDM blend matrices reinforced with different types of fibers can be modeled using the Avrami equation. On the other hand, the kinetic curves obtained under nonisothermal conditions provide a further confirmation of the nucleating action of the fibers on the PP crystallization. Optical polarizing microscopy was also used to investigate the effect of EPDM on the spherulite growth and the transcrystallinity phenomenon on the surface of the fibers. The results of such analysis showed that the transcrystallinity phenomenon is hindered at high rubber percentages. As in the case of the rate of crystallization, the highest proportion of transcrystallinity was observed in the presence of the aramidic fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1063–1074, 2001     

Melting behavior,isothermal and nonisothermal crystallization kinetics of PP/mLLDPE blends

Melting behavior, nonisothermal crystallization and isothermal crystallization kinetics of polypropylene (PP) with metallocene‐catalyzed linear low density polyethylene (mLLDPE) were studied by differential scanning calorimetry (DSC). The results show that PP and mLLDPE were partially miscible. The Avrami analysis was applied to analyze the nonisothermal and isothermal crystallization kinetics of the blends, the Mo Z.S. method was used to take a comparison in nonisothermal kinetics. Values of Avrami exponent indicate the crystallization nucleations of both pure PP and PP in the blends were heterogeneous, the growth of spherulites is tridimensional and the spherulites in the blends were more perfect than that in pure PP. The crystallization activation energy was estimated by Kissinger method and Arrhenius equation and the two methods draw similar results. The mLLDPE increased the crystallization rate of PP in nonisothermal crystallization process and decreased it in isothermal process. The results from nonisothermal crystallization and isothermal crystallization kinetics were not consistent because the two processes were completely different. Addition of minor mLLDPE phase favors to increase the overall crystallinity of PP, showing the mLLDPE entered the PP crystals. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide)

The isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide) (PA‐10T) was studied by differential scanning calorimetry. Several kinetic analyses were used to describe the crystallization process. The commonly used Avrami equation and the one modified by Jeziorny were used, respectively, to describe the primary stage of isothermal and nonisothermal crystallization. The Avrami exponent n was evaluated to be in the range of 2.36–2.67 for isothermal crystallization, and of 3.05–5.34 for nonisothermal crystallization. The Ozawa analysis failed to describe the nonisothermal crystallization behavior, whereas the Mo–Liu equation, a combination equation of Avrami and Ozawa formulas, successfully described the nonisothermal crystallization kinetics. In addition, the value of crystallization rate coefficient under nonisothermal crystallization conditions was calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 819–826, 2004     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

聚丙烯/共聚酯/蒙脱土复合材料结晶行为的研究

采用热台偏光显微镜研究了聚丙烯(PP)/共聚酯(COPET)以及PP/COPET/蒙脱土(MMT)复合材料等温结晶时的结晶形态,结果表明:两样品均呈现清晰的球晶所特有的黑十字消光图像,PP/COPET/MMT复合材料的球晶尺寸比PP/COPET样品的球晶尺寸大大减小。采用差示扫描量热法对PP/COPET以及PP/COPET/MMT复合材料的非等温结晶行为进行了研究,结果表明:随着MMT含量的增加,复合材料样品的结晶初始温度和结晶峰温基本呈现逐渐降低趋势,结晶放热焓随MMT含量增加先增加后减小;在不同的降温速率下结晶,两种样品结晶峰温均随降温速率的增大而降低,结晶放热焓也随着结晶速率的增大而降低。采用Jeniorny法处理了PP/COPET和PP/COPET/MMT样品的非等温结晶过程,得出了两体系的结晶速率总体上随着冷却速率的增加而加快,为多维结晶生长体系。     

Isothermal and nonisothermal crystallization kinetics of bio-sourced nylon 69☆

Bio-sourced nylon 69,one of promising engineering plastics,has a great potential in developing sustainable technology and various commercial applications.Isothermal and nonisothermal crystallization kinetics of nylon 69 is a base to optimize the process conditions and establish the structure–property correlations for nylon 69,and it is also highly bene ficial for successful applications of nylon products in industry.Isothermal and nonisothermal crystallization kinetics has been investigated by differential scanning calorimetry for nylon 69,bio-sourced even–odd nylon.The isothermal crystallization kinetics has been analyzed by the Avrami equation,the calculated Avrami exponent at various crystallization temperatures falls into the range of 2.28 and 2.86.In addition,the Avrami equation modi fied by Jeziorny and the equation suggested by Mo have been adopted to study the nonisothermal crystallization.The activation energies for isothermal and nonisothermal crystallization have also been determined.The study demonstrates that the crystallization model of nylon 69 might be a twodimensional(circular)growth at both isothermal and nonisothermal crystallization conditions.Furthermore,the value of the crystallization rate parameter(K)decreases signi ficantly but the crystallization half-time(t1/2)increases with the increase of the isothermal crystallization temperature.To nonisothermal crystallization,the crystallization rate increases as the cooling rate increases according to the analysis of Jeziorny's theory.The results of Mo's theory suggest that a faster cooling rate is required to reach a higher relative degree of crystallinity in a unit of time,and crystallization rate decreases when the relative degree of crystallinity increases at nonisothermal crystallization conditions.     

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。     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Crystallization and melting behaviour of polypropylene ‘catalloys’

The crystallization and melting behaviour of polypropylene ‘catalloys’ (PP‐cats) as well as pure polypropylene (PP) were investigated using differential scanning calorimetry. The results showed that, for PP‐cats and PP, a single melting peak of PP appeared under slow cooling rate. When the cooling rate is fast enough in the non‐isothermal case, or the crystallization temperature is relatively high in the isothermal case, a shoulder peak appears in front of the melting peak with increasing ethylene content in PP‐cats. It is believed that this shoulder is induced by recrystallization of crystals initially formed during non‐isothermal or isothermal crystallization. When the ethylene component in PP‐cats reached a certain level, there existed a melting peak of polyethylene (PE) crystallized during the cooling process. Polarized optical microscopy (POM) showed that the spherulites formed by PP‐cats were much smaller and had less perfect morphology compared with that formed by pure PP at the same cooling rate. And with the increase of the cooling rate, the spherulites could not be clearly observed. Copyright © 2004 Society of Chemical Industry     

Study on the crystallization kinetics of PP/GF composites

The crystallization kinetics and morphology of glass fiber-reinforced polypropylene (PP/GF) were investigated in this work. Both isothermal and nonisothermal crystallization behaviors of 90PP/10GF, 80PP/20GF, and 70PP/30GF were examined with a DSC instrument. It was found that the addition of glass fiber would increase the crystallization rate of PP and increase the content of β spherulite, which was most likely formed at temperatures between 390 and 400 K. The morphology of spherulites of PP/GF composites were examined with SEM and a polarized microscope. All experimental observations conformed rather well with the theoretical approach, a dynamic crystallization model, proposed in our previous work. The size of α spherulites of PP would decrease at lower crystallization temperature, or at higher cooling rate, or by adding glass fiber in it.     

Crystallization kinetics of poly(phenylene sulfide) (PPS) and PPS/carbon fiber composites

The evolution of crystallinity of neat PPS and of the carbon fiber reinforced polymer under different processing conditions is studied. Crystallization from the amorphous state at low temperatures (cold crystallization), crystallization from the melt during cooling, and crystal melting processes are analyzed using calorimetric techniques under both isothermal and nonisothermal conditions. Cold and melt crystallization kinetics are described using an Avrami equation and an Arrhenius expression for the temperature dependence of the kinetic constant. Also, the melting kinetics of the, reinforced and of the unreinforced polymer are studied in this work. The effect of carbon fibers on the crystallization kinetics of PPS is analyzed, and a comparison of the crystallization behavior of PPS and other semicrystalline thermoplastic matrices, such as poly(etheretherketone) (PEEK), is presented.     

Crystallization behavior of poly(ether ether ketone ketone)

The melting behavior of semicrystalline poly(ether ether ketone ketone) (PEEKK) has been studied by differential scanning calorimetry (DSC). When PEEKK is annealed from the amorphous state, it usually shows two melting peaks. The upper melting peaks arise first, and the lower melting peaks are developed later. The upper melting peaks shown in the DSC thermogram are the combination (addition) of three parts: initial crystal formed before scanning; reorganization; and melting-recrystallization of lower melting peaks in the DSC scanning period. In the study of isothermal crystallization kinetics, the Avrami equation was used to analyze the primary process of the isothermal crystallization; the Avrami constant, n, is about 2 for PEEKK from the melt and 1.5 for PEEKK from the glass state. According to the Lauritzen-Hoffman equation, the kinetic parameter of PEEKK from the melt is 851.5 K; the crystallization kinetic parameter of PEEKK is higher than that of PEEK, and suggests the crystallizability of PEEKK is less than that of PEEK. The study of crystallization on PEEKK under nonisothermal conditions is also reported for cooling rates from 2.5°C/min to 40°C/min, and the nonisothermal condition was studied by Mandelkern analysis. The results show the nonisothermal crystallization is different from the isothermal crystallization. © 1996 John Wiley & Sons, Inc.     

Dramatic influence of compatibility on crystallization behavior and morphology of polypropylene in NBR/PP thermoplastic vulcanizates

In this study, the isothermal/nonisothermal crystallization behavior of polypropylene (PP) in acrylonitrile butadiene rubber (NBR)/PP thermoplastic vulcanizates (TPVs) prepared with three different processing methods, the compatibility effect therein, and the mechanism involved were studied. We concluded that the vulcanized NBR particles in TPVs act as heterogeneous nucleation centers and increase the number of nuclei. The crystallization rate of PP thereby increases and the growth of PP spherulites is restrained because of the isolation of vulcanized NBR particles. Since the addition of compatibilizer improves the compatibility of NBR and PP, the smaller and uniformly dispersed NBR particles are obtained, resulting in more and smaller PP crystals as well as higher crystallization rate, compared with Ultra-fine fully vulcanized NBR particles (UFNBR)/PP TPV and NBR/PP TPV without compatibilization. The isothermal crystallization kinetics of PP in TPVs obeys the Avrami equation, whereas the nonisothermal crystallization kinetics is well described by the equation of Mo et al.     

Nonisothermal Crystallization Kinetics of Polypropylene/Polyethersulfone Blend

The nonisothermal crystallization kinetics of PP and PP/PES (80/20 wt%) blend was investigated by using differential scanning calorimetry (DSC). It was observed that the crystallization peak temperature (T_p) and the half time (t _1/2) of crystallization of PP/PES blend are slightly but consistently lower than those of PP at various cooling rates. The nonisothermal crystallization data were analyzed by using Avrami equation, Ozawa and Mo method. The validity of the different kinetics models to the nonisothermal crystallization process of two samples is discussed. The Mo method can successfully explain the overall nonisothermal crystallization process of PP and PP/PES blend. The activation energy (ΔE) for nonisothermal crystallization of PP and PP/PES blend is determined by using the Kissinger method. The result shows that the ΔE value of PP is slightly higher than that of PP/PES blend.     

Understanding the effect of silica nanoparticles and exfoliated graphite nanoplatelets on the crystallization behavior of isotactic polypropylene

This study explores how the presence of nanofillers with different structural and chemical characteristics, specifically silica nanoparticles and exfoliated graphite nanoplatelets (GNP), alters the crystallization behavior and polymorphism of a semicrystalline polymer, such as polypropylene (PP). The main focus of this research is to investigate how silica and GNP affect the nucleation and growth of PP crystals during isothermal crystallization. The nonisothermal crystallization behavior, including crystal structures, crystallization temperature, and rate, is also determined. PP composites with nanomaterial content up to 7 wt% were produced by melt mixing and injection molding. Both silica and graphite were found to be effective nucleating agents, significantly increasing the crystallization rate during isothermal crystallization, with greater changes observed in case of GNP composites. The effect of filler type and amount on the PP polymorphism and lamella thickness was studied by X‐ray diffraction and modulated differential scanning calorimetry. Both silica and graphite were found to be effective nucleating agents for the less common β‐phase of PP crystals even at low nanomaterial concentration. α‐?crystal perfection and the recrystallization of the β‐form in the α‐form and/or at the transcrystalline regime were found to be responsible for the recrystallization occurring upon melting in nanocomposites at high silica or medium GNP content. POLYM. ENG. SCI., 55:672–680, 2015. © 2014 Society of Plastics Engineers