Crystallization kinetics for simulation of processing of various polyesters

The approach to determine crystallization kinetic parameters based on the DSC nonisothermal crystallization experiments is applied to poly(butylene terephthalate) (PBT) and poly(ethylene‐2,6‐naphthalate) (PEN). The differential form of the Nakamura equation and master curve approach are used. The isothermal induction times are obtained from nonisothermal induction times according to the concept of induction time index. The correction of temperature lag between the DSC furnace and the sample is incorporated. The corrected nonisothermal crystallization kinetic data is shifted with respect to an arbitrarily chosen reference temperature to obtain the master curve. By fitting the obtained master curve with the Hoffman‐Lauritzen equation, the model parameters for the crystallization rate constant are obtained. The relative crystallinity measured at different cooling and heating rates is described by these model parameters. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2847–2855, 2006     

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     

Crystallization kinetics of high-density polyethylene/linear low-density polyethylene blend

This article presents crystallization kinetics studies on a cocrystallizing polymer highdensity polyethylene (HDPE)/linear lowd-ensity polyethylene (LLDPE) blend. The nonisothermal crystallization exotherms obtained by differential scanning calorimetry (DSC) were analyzed to investigate the effect of cocrystallization on kinetics parameters, namely the Avrami exponent and activation energy. The regular change of Avrami exponent with blend composition from a value of about 3 corresponding to HDPE to a value of 2 corresponding to LLDPE is observed. A sheaf-like crystalline growth with variation of nucleation depending on blend composition is concluded from these results of DSC exotherm analysis in conjunction with the small-angle light scattering observations. The observed variation of activation energy of crystallization with blend composition suggests the role of interaction of side chains and comonomer units present in the LLDPE. © 1994 John Wiley & Sons, Inc.     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

Quiescent polymer crystallization: Modelling and measurements

The problem of predicting nonisothermal crystallization kinetics based on isothermal data is considered, with reference to the difficulties involved, both experimental and theoretical. The kinetic model used is the differential form of the Nakamura equation which is an extension of the Avrami equation so as to apply to nonisothermal crystallization. Nonisothermal induction times are obtained from isothermal induction times according to the concept of induction time index. The theory of Hoffman Lauritzen is used to extrapolate the limited isothermal crystallization rate data. Good agreement between DSC (differential scanning calorimetry) nonisothermal crystallinity results and model predictions is obtained for our own data on poly(ethylene terephthalate) (PET) and some literature data on nylon-6, if the temperature lag between the sample and the DSC furnace is taken into account. The advantages of the present approach in process modeling are pointed out. Quenching experiments have also been performed in which PET slabs are allowed to cool and crystallize from the melt under quiescent conditions. The resulting crystallinity distributions in the thickness direction are measured and predicted by using kinetic parameter values obtained from isothermal DSC measurements alone.     

Formation and characterization of polyethylene blends for autoclave‐based expanded‐bead foams

Blends of linear‐low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and high‐ density polyethylene (HDPE) were foamed and characterized in this research. The goal was to generate clear dual peaks from the expanded polyethylene (EPE) foam beads made from these blends in autoclave processing. Three blends were prepared in a twin‐screw mixing extruder at two rotational speeds of 5 and 50 rpm: Blend1 (LLDPE with 20 wt% HDPE), Blend 2 (LLDPE with 20 wt% LDPE), and Blend 3 (LLDPE with 10 wt% HDPE and 10 wt% LDPE). The differential scanning calorimetric (DSC) measurement was taken at two cooling rates: 5 and 50°C/min. Although no dual peaks were present, the results showed that blending with HDPE has a more noticeable effect on the DSC curve of LLDPE than blending with LDPE. Also, the rotational speed and cooling rate affected the shape of the DSC curves and the percentage area below the onset point. The DSC characterization of the batch foamed blends revealed multiple peaks at certain temperatures, which may be mainly due to the annealing effect during the gas saturation process. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Isothermal crystallization kinetics and melting behavior of modified high‐density polyethylene/barium sulfate nanocomposites

The melting/crystallization behavior and isothermal crystallization kinetics of high‐density polyethylene (HDPE)/barium sulfate (BaSO₄) nanocomposites were studied with differential scanning calorimetry (DSC). The isothermal crystallization kinetics of the neat HDPE and nanocomposites was described with the Avrami equation. For neat HDPE and HDPE/BaSO₄ nanocomposites, the values of n ranges from 1.7 to 2.0. Values of the Avrami exponent indicated that crystallization nucleation of the nanocomposites is two‐dimensional diffusion‐controlled crystal growth. The multiple melting behaviors were found on DSC scan after isothermal crystallization process. The multiple endotherms could be attributed to melting of the recrystallized materials or the secondary lamellae caused during different crystallization processes. Adding the BaSO₄ nanoparticles increased the equilibrium melting temperature of HDPE in the nanocomposites. Surface free energy of HDPE chain folding for crystallization of HDPE/BaSO₄ nanocomposites was lower than that of neat HDPE, confirming the heterogeneous nucleation effect of BaSO₄. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Influence of nanofiller dimensionality on the crystallization behavior of HDPE/carbon nanocomposites

The isothermal and nonisothermal crystallization behavior of high density polyethylene (HDPE) containing various zero, one, and two dimensional (0‐D, 1‐D, and 2‐D) carbon nanofillers were investigated by means of differential scanning calorimetry. For a given temperature, the isothermal crystallization incubation time of HDPE became longer with the addition of lower dimensional carbon nanofillers, and the isothermal crystallization rate got slower. The values of Avrami and Tobin exponents indicated that the isothermal crystallization of HDPE followed two‐dimensional crystal growth in the presence of 2‐D and 1‐D carbon nanofillers, while exhibited three‐dimensional heterogeneous crystal growth in the presence of 0‐D carbon nanofillers. Contrary to the isothermal study, the nonisothermal crystallization of HDPE was accelerated in the presence of lower dimensional nanofillers. The nonisothermal crystallization data were finally analyzed using Ozawa and Mo methods. It was observed that only Mo approach could successfully describe the nonisothermal crystallization process of HDPE and HDPE/carbon nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of small amount of ultra high molecular weight component on the crystallization behaviors of bimodal high density polyethylene

In order to clarify the effect of high molecular weight component on the crystallization of bimodal high density polyethylene (HDPE), a commercial PE-100 pipe resin was blended with small loading of ultra high molecular weight polyethylene (UHMWPE). The isothermal crystallization kinetics and crystal morphology of HDPE/UHMWPE composites were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The presence of UHMWPE results in elevated initial crystallization temperature of HDPE and an accelerating effect on isothermal crystallization. Analysis of growth rate using Lauritzen-Hoffman model shows that the fold surface free energy (σ_e) of polymer chains in HDPE/UHMWPE composites was lower than that in neat HDPE. Morphological development during isothermal crystallization shows that UHMWPE can obviously promote the nucleation rate of HDPE. It should be reasonable to conclude that UHMWPE appeared as an effective nucleating agent in HDPE matrix. Rheological measurements were also performed and it is shown that HDPE/UHMWPE composites are easy to process and own higher melt viscosity at low shear rate. Combining with their faster solidification, gravity-induced sag in practical pipe production is expected to be effectively avoided.     

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.     

Thermal properties and crystallization behavior of polyolefin ternary blends

Crystallization behaviors, spherulite growth and structure, and the crystallization kinetics of polypropylene (PP)/ethylene‐α‐olefln copolymer (mPE)/high‐density polyethylene (HDPE) ternary blends and of mPE/HDPE binary blends have been studied using polarizing optical micrography (POM) and differential scanning calorimetry (DSC). In mPE/HDPE blends, large pendant groups of mPE disturbed spherulite growth of HDPE, leading to a different crystallite morphology and isothermal kinetics. Non‐isothermal properties, morphology, and isothermal crystallization kinetics of PP in ternary blends were significantly influenced by the composition and crystallization behavior of the mPE/HDPE binary blends as well as the crystallization condition. Polym. Eng. Sci. 44:1858–1865, 2004. © 2004 Society of Plastics Engineers.     

mLLDPE非等温结晶动力学研究

利用差示扫描量热仪(DSC)研究了茂金属线性低密度聚乙烯(mLLDPE)和传统线性低密度聚乙烯(LLDPE)的非等温结晶行为。采用Jeziorny法和莫志深法对所得的数据进行了分析。结果表明,采用莫志深法处理数据可得到较好的线性关系,且mLLDPE在相同的相对结晶度下的结晶速率低于LLDPE。     

Master curve approach to polymer crystallization kinetics

Nonisothermal crystallization kinetic data obtained from differential scanning calorimetry (DSC) for a poly(ethylene terephthalate) are corrected for the effects of temperature lag between the DSC sample and furnace using the method of Eder and Janeschitz-Kriegl which is based on experimental data alone without resort to any kinetic model. A method is presented for shifting the corrected nonisothermal crystallization kinetic data with respect to an arbitrarily chosen reference temperature to obtain a master curve. The method is based on experimental data alone without reference to any specific form of kinetic model. When the isothermal crystallization kinetic data for the same material are shifted with respect to the same reference temperature, a master curve is also obtained which overlaps to a large extent the corresponding master curve from nonisothermal data. It follows that nonisothermal DSC measurements provide the same crystallization kinetic information as isothermal DSC Measurements, only over a wider range of temperatures. The shift factors obtained from experimental data alone are compared in turn with the corresponding values calculated from the Avrami equation, the Hoffman-Lauritzen expression, and the Nakamura equation as a means of evaluating these models individually. It is concluded that the Avrami equation is very good at describing isothermal crystallization kinetics, the Hoffman-Lauritzen extrapolation of the limited isothermal data to a wide range of temperatures is quite good, and the Nakamura equation yields reliable crystallization kinetic information over a narrower range of temperatures than nonisothermal data alone without using any specific model.     

Effects of irradiation on the melting and crystallization behavior of ethylene polymers with different thermal history

Ethylene polymers, including HDPE, Ziegler–Natta‐catalyzed LLDPE (Z–N LLDPE), metallocene‐catalyzed LLDPE (m‐LLDPE), and LDPE were thermally treated by different procedures, that is, quenching, slow cooling, and thermal segregation. These PE samples, having different thermal histories, were then irradiated with various doses, that is, 0, 13, 35, and 70 Mrad, by gamma ray using a ⁶⁰Co radiation source. The melting and crystallization behaviors of these irradiated samples were studied by a differential scanning calorimeter (DSC). The effects of the thermal histories and irradiation on the polymers were evaluated by their melting temperatures (T_m), crystallization temperatures (T_c), and heat enthalpies (ΔH) in the heating and cooling scans. The results indicated that irradiation affects the samples having different thermal histories in different ways. The effects of the dosage on each kind of sample are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 536–544, 2003     

Quiescent nonisothermal crystallization kinetics of isotactic polypropylenes

Recently, a model was developed for the nonisothermal crystallization of normal alkanes with chain lengths between 30 and 50. The model was derived based on the fundamental equation of Ozawa for nonisothermal crystallization, the surface nucleation theory, and the growth rate theory for extended chain crystals. In this paper, the proposed model is modified and extended to the case of polymer crystallization. Experimental differential scanning calorimetry data for three isotactic polypropylene resins with different molecular weights are presented at five cooling rates from 2 to 40 K/min. Model predictions are in excellent agreement with the experimental data for the three polymers at low and high supercoolings.     

Nonisothermal crystallization behavior of LLDPE/glass fiber composite

The nonisothermal crystallization behavior of linear low-density polyethylene (LLDPE)/glass fiber (GF) composite was investigated by differential scanning calorimetry (DSC). It was observed that the crystallization temperature peak (T_p) of LLDPE composite containing 5.0 wt % GF (LLDPE/GF5) was higher than that of the pure LLDPE at various cooling rates. The half-time of crystallization (t_1/2) of LLDPE/GF5 composite was shortened under the effect of GF. The nonisothermal crystallization kinetics of LLDPE and LLDPE/GF5 composite were analyzed through the Avrami, Ozawa, and Mo equations. The results indicated that the data of the nonisothermal crystallization for LLDPE and LLDPE/GF5 composite calculated based on the Ozawa equation did not have the good linear relationship, but the nonisothermal crystallization behaviors of LLDPE and LLDPE/GF5 composite could be successfully described by the modified Avrami and Mo methods. The crystallization rate Z_c of the modified Avrami parameter of LLDPE/GF5 composite was higher than that of pure LLDPE at the same cooling rate. The Mo parameter F(T) of LLDPE/GF5 composite was lower than that of LLDPE at the same degree of crystallinity. Through the Kissinger equation, the activation energies E_d of LLDPE and LLDPE/GF5 composite were evaluated, and their values were 312.3 and 251.2 kJ/mol, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Non‐isothermal crystallization kinetics and segmental dynamics of high density polyethylene/butyl rubber blends

Non‐isothermal crystallization kinetics and dynamics of polymer blends are important to both theory and applications. In this work, we studied the morphology, crystal structure, non‐isothermal crystallization kinetics and dynamics of high density polyethylene/butyl rubber (HDPE/IIR) blends. The non‐isothermal crystallization kinetics is analyzed by Mo's model and the dynamics behavior is analyzed by a linear method. The results of morphology, non‐isothermal crystallization kinetics and dynamics show that the condensed structure of HDPE/IIR blends has a marked influence on their non‐isothermal crystallization kinetics and segmental dynamics. © 2015 Society of Chemical Industry     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000     

Implications of melt compatibility/incompatibility on thermal and mechanical properties of metallocene and Ziegler–Natta linear low density polyethylene (LLDPE) blends with high density polyethylene (HDPE): influence of composition distribution and branch content of LLDPE

In this paper, the implications of melt compatibility on thermal and solid‐state properties of linear low density polyethylene/high density polyethylene (LLDPE/HDPE) blends were assessed with respect to the effect of composition distribution (CD) and branch content (BC). The effect of CD was studied by melt blending a metallocene (m‐LLDPE) and a Ziegler‐Natta (ZN) LLDPE with the same HDPE at 190 °C. Similarly, the effect of BC was examined. In both cases, resins were paired to study one molecular variable at a time. Thermal and solid‐state properties were measured in a differential scanning calorimeter and in an Instron mechanical testing instrument, respectively. The low‐BC m‐LLDPE (BC = 14.5 CH₃/1000 C) blends with HDPE were compatible at all compositions: rheological, thermal and some mechanical properties followed additivity rules. For incompatible high‐BC (42.0 CH₃/1000 C) m‐LLDPE‐rich blends, elongation at break and work of rupture showed synergistic effects, while modulus was lower than predictions of linear additivity. The CD of LLDPE showed no significant effect on thermal properties, elongation at break or work of rupture; however, it resulted in low moduli for ZN‐LLDPE blends with HDPE. For miscible blends, no effect for BC or CD of LLDPE was observed. The BC of LLDPE has, in general, a stronger influence on melt and solid‐state properties of blends than the CD. Copyright © 2004 Society of Chemical Industry     

Co‐crystallization in ternary polyethylene blends: tie crystal formation and mechanical properties improvement

Understanding the co‐crystallization behavior of ternary polyethylene (PE) blends is a challenging task. Herein, in addition to co‐crystallization behavior, the rheological and mechanical properties of melt compounded high density polyethylene (HDPE)/low density polyethylene (LDPE)/Zeigler ? Natta linear low density polyethylene (ZN‐LLDPE) blends have been studied in detail. The HDPE content of the blends was kept constant at 40 wt% and the LDPE/ZN‐LLDPE ratio was varied from 0.5 to 2. Rheological measurements confirmed the melt miscibility of the entire blends. Study of the crystalline structure of the blends using DSC, wide angle X‐ray scattering, small angle X‐ray scattering and field emission SEM techniques revealed the formation of two distinct co‐crystals in the blends. Fine LDPE/ZN‐LLDPE co‐crystals, named tie crystals, dispersed within the amorphous gallery between the coarse HDPE/ZN‐LLDPE co‐crystals were characterized for the first time in this study. It is shown that the tie crystals strengthen the amorphous gallery and play a major role in the mechanical performance of the blend.© 2016 Society of Chemical Industry