Evaluation of nonisothermal crystallization kinetic models for linear poly(phenylene sulfide)

The nonisothermal crystallization kinetics of linear Poly(phenylene sulfide) (PPS) was studied with differential scanning calorimetry. Ozawa theory, Jeziorny model, and Mo equation were applied to describe the crystallization kinetics and to determine the crystallization parameters and mechanism of the linear PPS resin. The crystallization activation energies were also calculated using Kissinger formula and Flynn‐Wall‐Ozawa equation, respectively. According to the Ozawa model, it is found that instantaneous nucleation takes place during crystallization of PPS; the Ozawa exponent m is 3 in initial stage of crystallization; as the crystallization temperature decreases, the value of m reduces, and the growth rate of crystal almost keeps a constant. The Avrami exponent n obtained from Jeziorny model fluctuate around 1.84. Based on the Jeziorny model, the crystallization rate increases with increasing the cooling rate, but it does not change any longer when the cooling rate rise to a certain value. Mo equation also exhibits great advantages in treating the nonisothermal crystallization kinetics of PPS. The activation energy E of nonisothermal crystallization process of PPS is calculated to be −162.73 kJ/mol by the Kissinger formula, and the mean value of E determined by Flynn‐Wall‐Ozawa equation is −152.40 kJ/mol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

NONISOTHERMAL CRYSTALLIZATION KINETICS AND MECHANICAL PROPERTIES OF PP/NANO-SiO2 COMPOSITES

The nonisothermal crystallization kinetics of polypropylene (PP)/nano-SiO₂ composites was studied by means of differential scanning calorimetry (DSC). The modified Avrami theories by Jeziorny, Ozawa, and Mo were used to analyze the data of DSC. The results showed that both the Jeziorny and Mo methods could describe this system very well, but the Ozawa analysis failed. The activation energy was evaluated by the Kissinger method. It was found that the crystallization activation energy of PP was higher than that of PP/nano-SiO₂ composites. The determined results of mechanical properties showed that the addition of nano-SiO₂ increased the mechanical properties of the PP. Micrographs of Polarized optical micrograph (POM) further demonstrated that nano-SiO₂ could toughen the PP.     

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     

La_2O_3/LDPE复合材料非等温结晶性能研究

利用差示扫描量热仪(DSC)考察了氧化镧(La2O3)/低密度聚乙烯(LDPE)复合材料的非等温结晶行为。通过Jeziorny法、Ozawa法及莫志深法研究了复合材料的非等温结晶动力学。结果表明:在添加La2O3后,LDPE成核速率降低,结晶度下降,晶体粒径分布变宽。在非等温结晶动力学分析中,Jeziorny法lg[-ln(1-Xt)]～lgt关系曲线在结晶前期和中期具有较好的线性关系,结晶后期产生较大偏离;Ozawa法并不适用;而莫志深法适用于该体系的研究,表明La2O3的加入使LDPE结晶速率增大。     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystal morphology and nonisothermal crystallization kinetics of short carbon fiber/poly(trimethylene terephthalate) composites

The crystal morphology and nonisothermal crystallization kinetics of short carbon fiber/poly(trimethylene terephthalate) (SCF/PTT) composites were investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The optical micrographs suggest that the more content of SCF in composites, the smaller size of the spherulites is. Moreover, the addition of SCF can lead to forming banded spherulites in composites. The Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of nonisothermal crystallization of various composites. The results suggest that the SCF served as nucleation agent, accelerates the crystallization rate of the composites, and the more content of SCF, the faster crystallization rate is. Effective activation energy calculated by the differential iso‐conversional method developed by Friedman also concludes that the composite with more SCF component has higher crystallization ability than that with less SCF content. The kinetic parameters U* and K_g are determined, respectively, by the Hoffman–Lauritzen theory. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonisothermal crystallization behavior of biodegradable poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) copolyester

A series of biodegradable aliphatic‐aromatic copolyester, poly(butylene terephthalate‐co‐butylene adipate‐co‐ethylene terephthalate‐co‐ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4‐butanediol (BG) and ethylene glycol (EG) by direct esterification and polycondensation. The nonisothermal crystallization behavior of PBATE copolyesters was studied by the means of differential scanning calorimeter, and the nonisothermal crystallization kinetics were analyzed via the Avrami equation modified by Jeziorny, Ozawa analysis and Z.S. Mo method, respectively. The results show that the crystallization peak temperature of PBATE copolyesters shifted to lower temperature at higher cooling rate. The modified Avrami equation could describe the primary stage of nonisothermal crystallization of PBATE copolyesters. The value of the crystallization half‐time (t_1/2) and the crystallization parameter (Z_c) indicates that the crystallization rate of PBATE copolyesters with more PTA content was higher than that with less PTA at a given cooling rate. Ozawa analysis was not suitable to study the nonisothermal crystallization process of PBATE copolyesters, but Z.S. Mo method was successful in treatingthis process. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

PA11/SiC复合材料非等温结晶动力学研究

通过熔融共混法制备了尼龙11/碳化硅(PA11/SiC)复合材料,利用差示扫描量热仪(DSC)研究了该复合材料的非等温结晶过程,且采用Avrami方程修正的Jeziorny法和Mo法对其非等温结晶动力学进行了研究,并计算得到相关非等温结晶动力学参数。结果表明:Jeziorny法和Mo法都适用于处理PA11及PA11/SiC复合材料的非等温结晶过程,其分析结果均显示,SiC的加入影响了PA11复合材料的非等温结晶行为,少量(1%)SiC的加入促进了PA11复合材料的成核及晶体生长,提高了结晶速率;由Jeziorny法可知,PA11及其复合材料的非等温过程可分为初期结晶和二次结晶两个阶段,在二次结晶阶段,结晶方式为一维线性、二维盘状和三维球晶生长并存。     

Non-isothermal crystallization kinetics of poly (lactic acid)/modified carbon black composite

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. Jeziorny equation, the Ozawa model and Mo equation were employed to describe the non-isothermal crystallization process of poly (lactic acid) (PLA), PLA/CB and PLA/modified carbon black (MCB) composites. It is found that the Ozawa model fail to describe the non-isothermal crystallization process for PLA and its composites, while Jeziorny equation and Mo’s theory provide a good fitting. The comparison of crystallization kinetics between PLA/MCB and PLA through Lauritzen–Hoffman model indicates that there appears a transition from regimes II to III in PLA and PLA/MCB. The fold surface free energy σ _e of PLA/MCB composite is higher than that of neat PLA, implying that the existence of nucleating agent is unfavorable for the regular folding of the molecule chain.     

Morphology,Crystallization and Dynamical Mechanical Behavior of iPP/Nano-CaCO3 Composites

This article describes our study of crystallization behavior of nano-CaCO₃-filled polypropylene under nonisothermal from the melt by differential scanning calorimetry (DSC). Morphology observation indicated with increasing CaCO₃ content the aggregates increased. Nano-CaCO₃ acted as nucleating site during nonisothermal crystallization in all iPP/nano-CaCO₃ composites. For nonisothermal crystallization kinetic studies, the result indicated that the Jeziorny and Ozawa approach cannot adequately describe the nonisothermal crystallization kinetic of iPP composite. In addition, Mo equation was employed to describe the nonisothermal crystallization kinetic process with satisfied results. Dynamic mechanical analysis indicated with increasing CaCO₃ content the glass transition decreased slightly.     

PP/PP-g-MAH/HGB复合材料非等温结晶行为研究

采用熔融法制备了聚丙烯/马来酸酐接枝聚丙烯/空心玻璃微珠（PP/PP-g-MAH/HGB）复合材料,采用差示扫描量热仪研究了PP、PP/HGB、PP/PP-g-MAH/HGB复合材料的非等温结晶过程,并通过Jeziorny法和Mo法研究了3种材料的非等温结晶动力学。结果表明,随着降温速率的增大,3种材料的结晶峰温、结晶起始温度和结晶度均减小,结晶速率增大;HGB抑制了PP的结晶行为,降低了结晶速率;PP-g-MAH对PP结晶速率的影响较小,HGB和PP-g-MAH都会改变PP的结晶成核和生长机理。     

Isothermal and nonisothermal crystallization kinetics of nylon-11

Analysis of the isothermal, and nonisothermal crystallization kinetics of Nylon-11 is carried out using differential scanning calorimetry. The Avrami equation and that modified by Jeziorny can describe the primary stage of isothermal and nonisothermal crystallization of Nylon-11. In the isothermal crystallization process, the mechanism of spherulitic nucleation and growth are discussed; the lateral and folding surface free energies determined from the Lauritzen–Hoffman equation are ς = 10.68 erg/cm² and ς_e = 110.62 erg/cm²; and the work of chain folding q = 7.61 Kcal/mol. In the nonisothermal crystallization process, Ozawa analysis failed to describe the crystallization behavior of Nylon-11. Combining the Avrami and Ozawa equations, we obtain a new and convenient method to analyze the nonisothermal crystallization kinetics of Nylon-11; in the meantime, the activation energies are determined to be −394.56 and 328.37 KJ/mol in isothermal and nonisothermal crystallization process from the Arrhonius form and the Kissinger method. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2371–2380, 1998     

LLDPE/粉煤灰复合材料非等温结晶动力学研究简

利用差示扫描量热法（DSC）结合Avrami方程研究了线性低密度聚乙烯（LLDPE）、LLDPE/Fly Ash（粉煤灰）的非等温结晶动力学.通过Jeziomy法、Ozawa法和莫志深法分别对非等温结晶过程进行处理,采用Kissinger法和Takhor法得到迁移活化能.结果显示,粉煤灰粉体的加入阻碍了LLDPE分子链的规则排列,影响了链段的结晶扩散迁移规整排列,使LLDPE的结晶速率变慢,对LLDPE晶体生长起了抑制作用.由Ozawa法分析实验数据,得到的线性关系很差,因此也很难得到可靠的动力学参数.在所有结晶速率下,样品的Avrami指数n值在1.42 ～2.09之间变化,说明粉煤灰的加入对LLDPE的成核与生长方式的影响有限.用莫志深法得出的结论与Jeziorny法一致,b值在0.76～1.13之间变化.     

Nonisothermal crystallization behavior of highly exfoliated polypropylene/clay nanocomposites prepared by in situ polymerization

Polypropylene/clay nanocomposites (PPCNs) were prepared via an in situ polymerization method with a Ziegler–Natta/clay compound catalyst in which the MgCl₂/TiCl₄ catalyst was embedded in the clay galleries. The wide‐angle X‐ray diffraction and transmission electron microscopy results showed that the clay particles were highly exfoliated in the polypropylene (PP) matrix. The nonisothermal crystallization kinetics of these PPCNs were investigated by differential scanning calorimetry at various cooling rates. The nucleation activity were calculated by Dobreva's method to demonstrate that the highly dispersed silicate layers acted as effective nucleating agents. The Avrami, Jeziorny, Ozawa, and Mo methods were used to describe the nonisothermal crystallization behavior of the PP and PPCNs. Various parameters of nonisothermal crystallization, such as the crystallization half‐time, crystallization rate constant, and the kinetic parameter F(t), reflected that the highly exfoliated silicate layers significantly accelerated the crystallization process because of its outstanding nucleation effect. The activation energy values of the PP and PPCNs determined by the Kissinger method increased with the addition of the nanosilicate layers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization kinetics,melting behavior,and morphologies of poly(butylene succinate) and poly(butylene succinate)‐block‐poly(propylene glycol) segmented copolyester

This article investigated the crystallization kinetics, melting behavior, and morphologies of poly(butylene succinate)(PBS) and its segmented copolyester poly(butylene succinate)‐block‐poly(propylene glycol)(PBSP) by means of differential scanning calorimetry, polarized light microscopy, and wide angle X‐ray diffraction. Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the Avrami equation modified by Jeziorny, and the model combining Avrami equation and Ozawa equation were employed. The results showed that the introduction of poly(propylene glycol) soft segment led to suppression of crystallization of PBS hard segment. The melting behavior of the isothermally and nonisothermally crystallized samples was also studied. Results showed that the isothermally crystallized samples exhibited two melting endotherms, whereas only one melting endotherm was shown after nonisothermal crystallization. The spherulitic morphology of PBSP and wide angle X‐ray diffraction showed that the polyether segments were excluded from the crystals and resided in between crystalline PBS lamellae and mixed with amorphous PBS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nonisothermal crystallization behavior of a luminescent conjugated polymer,poly(9,9‐dihexylfluorene‐alt‐2,5‐didodecyloxybenzene)

The nonisothermal crystallization kinetics of poly(9,9‐dihexylfluorene‐alt‐2,5‐didodecyloxybenzene) (PF6OC12) from the melt were investigated using differential scanning calorimetry under different cooling rates. Several analysis methods were used to describe the nonisothermal crystallization behavior of PF6OC12. It was found that the modified Avrami method by Jeziorny was only valid for describing the early stage of crystallization but was not able to describe the later stage of PF6OC12 crystallization. Also, the Ozawa method failed to describe the nonisothermal crystallization behavior of PF6OC12. However, the method developed by combining the Avrami and Ozawa equations could successfully describe the nonisothermal crystallization kinetics of PF6OC12. According to the Kissinger method, the activation energy was determined to be 114.9 kJ mol^?1 for the nonisothermal melt crystallization of PF6OC12. Copyright © 2006 Society of Chemical Industry     

Nonisothermal and isothermal crystallization kinetics of nylon‐12

The isothermal and nonisothermal crystallization behavior of Nylon 12 was investigated using differential scanning calorimetry (DSC). An Avrami analysis was used to study the isothermal crystallization kinetics of Nylon 12, the Avrami exponent (n) determined and its relevance to crystal growth discussed and an activation energy for the process evaluated using an Arrhenius type expression. The Lauritzen and Hoffman analysis was used to examine the spherulitic growth process of the primary crystallization stage of Nylon 12. The surface‐free energy and work of chain folding were calculated using a procedure reported by Hoffmann and the work of chain folding per molecular fold (σ) and chain stiffness of Nylon 12 (q) was calculated and compared to values reported for Nylons 6,6 and 11. The Jeziorny modification of the Avrami analysis, Cazé and Chuah average Avrami parameter methods and Ozawa equation were used in an attempt to model the nonisothermal crystallization kinetics of Nylon 12. A combined Avrami and Ozawa treatment, described by Liu, was used to more accurately model the nonisothermal crystallization kinetics of Nylon 12. The activation energy for nonisothermal crystallization processes was determined using the Kissinger method for Nylon 12 and compared with values reported previously for Nylon 6,6 and Nylon 11. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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