Multiple melting endotherms in melt‐crystallized nylon 10,12

The melting behaviour of melt‐crystallized nylon 10,12 was investigated by differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). The results show that all nylon 10,12 crystals obtained under various conditions, including isothermal, non‐isothermal and stepwise crystallization, and also after partial melting or annealing, show multiple melting behaviour. It was found that each melting endotherm has a different origin. The highest melting peak corresponds to melting of the recrystallized material while the other melting endotherms are related to melting of lamellae with different thicknesses developing under different crystallization conditions. The equilibrium melting point of nylon 10,12 was also firstly estimated to be about 206 °C. © 2001 Society of Chemical Industry     

Melting behavior,isothermal and nonisothermal crystallization kinetics of nylon 1111

The isothermal and nonisothermal crystallization kinetics of nylon 1111 was extensively studied using differential scanning calorimetry (DSC). The equilibrium melting temperature of nylon 1111 was determined to be 188°C. In this article, the Avrami equation was used to describe the isothermal crystallization behavior of nylon 1111. On the basis of the DSC results, the Avrami exponent, n, was determined to be around 3 during the isothermal crystallization process. Nonisothermal crystallization was analyzed using both the Avrami equation as modified by Jeziorny and an equation suggested by Mo. The larger value of the Avrami exponent, n, during the nonisothermal crystallization process indicates that the development of nucleation and crystal growth are more complicated during the nonisothermal crystallization for nylon 1111, and that the nucleation mode might simultaneously include both homogeneous and heterogeneous nucleations. The isothermal and nonisothermal crystallization activation energies of nylon 1111 were determined to be ?132 kJ/mol and ?121 kJ/mol using the Arrhenius equation and the Kissinger method, respectively. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Melting behaviors, isothermal and non-isothermal crystallization kinetics of nylon 1212

Isothermal crystallization, subsequent melting behavior and non-isothermal crystallization of nylon 1212 samples have been investigated in the temperature range of 160-171 °C using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited three melting endotherms. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallizations of nylon 1212. The Avrami exponent n was evaluated, and was found to be in the range of 1.56-2.03 for isothermal crystallization, and of 2.38-3.05 for non-isothermal crystallization. The activation energies (ΔE) were determined to be 284.5 KJ/mol and 102.63 KJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius' and the Kissinger's methods.     

Isothermal and nonisothermal crystallization kinetics of novel even‐odd nylon 10 11

Isothermal and nonisothermal crystallization kinetics of even‐odd nylon 10 11 were investigated by differential scanning calorimetry (DSC). Equilibrium melting point was determined to be 195.20°C. Avarmi equation was adopted to describe isothermal and nonisothermal crystallization. A new relation suggested by Mo was used to analyze nonisothermal crystallization and gave a good result. The crystallization activation energies have been obtained to be ?583.75 and ?270.06 KJ/mol for isothermal and nonisothermal crystallization, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1637–1643, 2005     

Kinetics of isothermal and nonisothermal crystallization of nylon 1313

The crystallization process of a new polyamide, nylon 1313, from the melt has been thoroughly investigated under isothermal and nonisothermal conditions. During isothermal crystallization, relative crystallinity develops in accordance with the Avrami equation with the exponent n ≈ 2 based on DSC analysis. Under nonisothermal conditions, several different analysis methods were used to elucidate the crystallization process. The Avrami exponent n is greater in the isothermal crystallization process, indicating that the mode of nucleation and the growth of the nonisothermal crystallization for nylon 1313 are more complicated, and that the nucleation mode might include both homogeneous and heterogeneous nucleation simultaneously. The calculated activation energy is 214.25 kJ/mol for isothermal crystallization by Arrhenius form and 135.1 kJ/mol for nonisothermal crystallization by Kissinger method, respectively. In addition, the crystallization ability of nylon 1313 was assessed by using the kinetic crystallizability parameters G. Based on this parameter, the crystallizability of many different polymers was compared theoretically. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1415–1422, 2007     

MCPA6/纳米TiO2原位复合材料的熔融行为

采用差示扫描量热法(DSC)研究了铸型尼龙6(MCPA6)及其纳米TiO2原位复合材料的等温结晶与非等温结晶晶体的熔融行为。结果表明：MCPA6／纳米TiO2原位复合材料等温结晶晶体的熔融行为呈现三重熔融峰，非等温结晶晶体的熔融行为呈现二重熔融峰；其高温熔融峰温随等温结晶温度或降温速率的变化基本不变，而低温熔融峰温则随等温结晶温度的升高或降温速率的减小而提高；纳米TiO2的加入对MCPA6有一定的成核作用，使其熔点提高。     

Isothermal and nonisothermal crystallization kinetics of MC nylon and polyazomethine/MC nylon composites

Crystallization kinetics of MC nylon (PA6) and polyazomethine (PAM)/MC nylon (PAM/PA6) both have been isothermally and nonisothermally investigated by different scanning calorimetry (DSC). Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The Avrami equation and Mo's modified method can describe the primary stage of isothermal and nonisothermal crystallization of PA6 and PAM/PA6 composite, respectively. In the isothermal crystallization process, the values of the Avrami exponent are obtained, which range from 1.70 to 3.28, indicating an average contribution of simultaneous occurrence of various types of nucleation and growth of crystallization. The equilibrium melting point of PA6 is enhanced with the addition of a small amount of rigid rod polymer chains (PAM). In the nonisothermal crystallization process, we obtain a convenient method to analyze the nonisothermal crystallization kinetics of PA6 and PAM/PA6 composites by using Mo's method combined with the Avrami and Ozawa equations. In the meanwhile, the activation energies are determined to be ?306.62 and ?414.81 KJ/mol for PA6 and PAM/PA6 (5 wt %) composite in nonisothermal crystallization process from the Kissinger method. Analyzing the crystallization half‐time of isothermal and nonisothermal conditions, the over rate of crystallization is increased significantly in samples with a small content of PAM, which seems to result from the increased nucleation density due to the presence of PAM rigid rod chain polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2844–2855, 2004     

Crystallization kinetics and melting behavior of nylon 10,10 in nylon 10,10–montmorillonite nanocomposites

The crystallization kinetics and melting behavior of nylon 10,10 in neat nylon 10,10 and in nylon 10,10–montmorillonite (MMT) nanocomposites were systematically investigated by differential scanning calorimetry. The crystallization kinetics results show that the addition of MMT facilitated the crystallization of nylon 10,10 as a heterophase nucleating agent; however, when the content of MMT was high, the physical hindrance of MMT layers to the motion of nylon 10,10 chains retarded the crystallization of nylon 10,10, which was also confirmed by polarized optical microscopy. However, both nylon 10,10 and nylon 10,10–MMT nanocomposites exhibited multiple melting behavior under isothermal and nonisothermal crystallization conditions. The temperature of the lower melting peak (peak I) was independent of MMT content and almost remained constant; however, the temperature of the highest melting peak (peak II) decreased with increasing MMT content due to the physical hindrance of MMT layers to the motion of nylon 10,10 chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2181–2188, 2003     

Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

氯化钙对尼龙6/66结晶态结构的影响

本文采用示差扫描量热法(DSC)、傅立叶变换红外光谱法(FTIR)研究了CaCl2对尼龙6/66结晶态结构的影响.DSC测试结果表明,随着尼龙6/66中CaCl2含量的增加,尼龙6/66的结晶温度、熔融温度降低,结晶度逐渐减小直至变为无定型态.红外光谱研究结果证实了钙离子能够插入尼龙6/66分子链,与尼龙6/66分子链上的羰基发生络合作用,破坏尼龙6/66原有的氢键,阻碍尼龙6/66分子链的自由运动,从而使其无法结晶.     

Primary and secondary crystallization kinetic analysis of nylon 1212

The isothermal and non‐isothermal melt‐crystallization kinetics of nylon 1212 were investigated by differential scanning calorimetry. Primary and secondary crystallization behaviors were analysed based on different approaches. The results obtained suggested that primary crystallization under isothermal conditions involves three‐dimensional spherulite growth initiated by athermal nucleation, while under non‐isothermal conditions, the mechanism of primary crystallization is more complex. Secondary crystallization displays a lower‐dimensional crystal growth, both in the isothermal and non‐isothermal processes. The crystallite morphology of nylon 1212, isothermally crystallized at various temperatures, was observed by polarized optical microscopy. The activation energies of crystallization under isothermal and non‐isothermal conditions were also calculated based on different approaches. Copyright © 2004 Society of Chemical Industry     

The effects of a nucleating agent and of fibers on the crystallization of nylon 66 matrices

Crystallization from the melt of nylon 66 in the presence of carbon fiber, aramid fiber, or nucleating agent was studied using differential scanning calorimetry (DSC) and hot stage microscopy. The use of the nucleating agent resulted in an increase in crystallization rate and a decrease of induction time under both isothermal and nonisothermal conditions. The fibers were found to behave like a giant nucleating site producing a uniform transcrystalline layer having morphology and crystallization kinetics different from those of the bulk matrix. The influence of the cooling rate on the process of nonisothermal crystallization was analyzed, and the values of activation energy, calculated from the cooling rate—crystallization temperature relationship, appeared to be higher for the nucleated and for the reinforced nylon compared with that of the neat nylon 66. This implied that the presence of fibers or nucleating agent led to the development of a more ordered structure, which required a larger amount of energy for crystallization.     

Isothermal and nonisothermal crystallization kinetics of nylon 10 12

This article studied the crystallization behaviors of a newly industrialized polyamide, Nylon 10 12, under isothermal and nonisothermal conditions from the melt. A differential scanning calorimeter (DSC) was used to monitor the energetics of the crystallization process. During isothermal crystallization, relative crystallinity develops in accordance with the time dependence described by the Avrami equation with the exponent n=2.0. For nonisothermal studies, several different analysis methods were used to describe the crystallization process. The experimental results show that the Ozawa approach cannot adequately describe the nonisothermal crystallization kinetics. However, Avrami treatment for nonisothermal crystallization is able to describe the system very well. The calculated activation energy is 264.4 KJ/mol for isothermal crystallization by Arrhenius form and 235.5 KJ/mol for nonisothermal crystallization by Kissinger method.     

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     

Melting behavior and isothermal crystallization kinetics of nylon 11/EVOH/dicumyl peroxide blends

Nylon 11/ethylene‐vinyl alcohol/dicumyl peroxide (DCP) blends were prepared using a single‐screw extruder. The melting behavior and isothermal crystallization kinetics were investigated using differential scanning calorimetry. The reorganization of nylon 11 crystals is strongly hindered owing to cocrosslinking phenomena. The analysis of the crystallization kinetics demonstrated that the Avrami equation well described the isothermal crystallization process of the primary stage. The spherulites growth kinetics parameters and fold surface free energy were also evaluated. The experimental results confirmed that the presence of DCP increased the crystallization rate. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

良好分散尼龙6/多壁碳纳米管复合材料的研究

采用柔和混合法制备纳米粒子良好分散的尼龙-6/多壁碳纳米管(PA6/MWNTs)复合材料,采用差示扫描量热仪(DSC)和广角X射线衍射法(XRD)研究了MWNTs对PA6基体结晶熔融行为的影响。DSC结果表明,MWNTs的加入大幅度地提高了PA6的结晶温度(最高提高约20℃),基体的结晶度也有所提高,说明良好分散的MWNTs在PA6结晶过程中呈现明显的异相成核作用;XRD结果证实,分散良好的MWNT促进PA6形成α晶型,抑制γ晶型的形成。同时,MWNT的加入导致复合材料出现熔融双峰现象,其形状随MWNT含量的变化而改变,双峰结构可能是由于熔融过程中伴随着重结晶而引起的。     

Investigation of melting behaviors and crystallinity of linear polyamide with high‐aliphatic content

The melting behaviors and crystal structures of a long alkyl chain polyamide and nylon 18 18, were investigated under annealing and isothermal crystallization conditions. Nylon 18 18 showed multiple melting peaks in differential scanning calorimetry (DSC) thermograms depending on thermal history of the samples. The origin of the multiple melting peaks may be a result of a melting and recrystallization mechanism during DSC scans. Wide‐angle X‐ray diffraction patterns showed two new diffraction peaks, which appeared at 0.44 and 0.37 nm, and are characteristic peaks of α‐form (triclinic structure) of even–even nylons with increasing annealing temperature. The intensities of these peaks increased, and they split further apart, with elevated annealing temperatures. The solid‐state ¹⁵N CP/MAS NMR spectra of the nylon 18 18 samples that had been quenched and annealed also confirmed the α‐crystalline form. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

氯化锂对尼龙6结构与性能影响的研究

用熔融共混法制备了尼龙6与氯化锂的共混物,采用DSC、XRD、测定熔体流动速率等方法研究了样品的结构与性能。结果表明加入氯化锂能够明显地改变尼龙6的结晶性能,使分子间作用力增强,玻璃化转变温度升高和熔体黏度增大。     

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.