不饱和聚酯/粘土纳米复合材料的制备与性能

为了改善不饱和聚酯树脂的力学性能,将有机改性的蒙脱土与苯乙烯均匀混合后再掺合到不饱和聚酯(UP)中,制备了不同粘土含量的不饱和聚酯树脂/粘土(UPR/Clay)纳米复合材料。差热分析发现随着粘土含量的增加,玻璃化温度有所增加。X射线衍射数据表明,纳米复合材料中粘土原有的峰基本消失,表明粘土结构层间距增大,结合透射电镜(TEM),确定此纳米复合材料为插层和剥离结构。冲击试验发现随着粘土加入冲击强度有一最大值。     

Crystallization behavior of poly(L‐lactic acid)/montmorillonite nanocomposites

In this study, we modified montmorillonite (MMT) with dilauryl dimethyl ammonium bromide (DDAB) and then exfoliated the structures in a poly(L ‐lactic acid) (PLLA) matrix. We used polar optical microscopy and X‐ray diffraction (XRD) to examine the morphologies of the resulting composites, differential scanning calorimetry to study the melting and crystallization behavior, and Fourier transform infrared (FTIR) and Raman spectroscopy to measure the influence of the intermolecular interactions between PLLA and MMT on the isothermal crystallization temperature. We found that the DDAB‐modified MMT was distributed uniformly in the PLLA matrix. At temperatures ranging from 130 to 140°C, the crystalline morphology resembled smaller Maltese cross‐patterned crystallites; at temperatures from 150 to 170°C, however, the number of crystallites decreased, their sizes increased, and they possessed ringed spherulite structures. In the XRD spectra, the intensity of the diffraction peaks of the 200/110 and 203 facets of the PLLA/MMT nanocomposites decreased as the crystallization temperature increased. In the FTIR spectra, the absorption peak of the C?O groups split into two signals at 1748 and 1755 cm^?1 when the isothermal crystallization temperature was higher than 140°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

氯丁橡胶/有机黏土纳米复合材料应变诱导结晶行为

通过熔体插层法制备氯丁橡胶/有机黏土纳米复合材料(CRCNs),利用偏光显微镜观察CRCNs在不同应变条件下微观结构的变化。主要研究有机黏土对CRCNs应变诱导结晶行为的影响,并通过XRD和SEM表征了CRCNs的微观结构。结果表明: 当有机黏土含量为5 phr时,CRCNs的综合力学性能最优。随着应变的增加,CRCNs的应力也在增加;当应变达到一定值时, CRCNs的应力迅速增加,应变诱导结晶集中产生。随着有机黏土含量的增加, CRCNs拉伸诱导结晶行为在高应变条件下产生。分析原因是氯丁橡胶基体中有机黏土与橡胶分子的插层结构逐渐减少,诱导结晶能力变弱。     

Fracture behavior of thermoplastic polyolefin/clay nanocomposites

A thermoplastic polyolefin (TPO) containing 70 wt % styrene–ethylene–butadiene‐styrene‐g‐maleic anhydride and 30 wt % polypropylene and its nanocomposites reinforced with 0.3–1.5 wt % organoclay were prepared by melt mixing followed by injection molding. The mechanical and fracture behaviors of the TPO/clay nanocomposites were investigated. The essential work of fracture (EWF) approach was used to evaluate the tensile fracture behavior of the nanocomposites toughened with elastomer. Tensile tests showed that the stiffness and tensile strength of TPO was enhanced by the addition of low loading levels of organically modified montmorillonite. EWF measurements revealed that the fracture toughness of the TPO/clay nanocomposites increased with increasing clay content. The organoclay toughened the TPO matrix of the nanocomposites effectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization behavior of nylon 11/montmorillonite nanocomposites under annealing

Exfoliated nylon 11/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization by the dispersion of organically modified MMT in 11‐aminoundecanoic acid monomer. The polymorphic behavior of the nylon 11/MMT nanocomposites was investigated with X‐ray diffraction, transmission electron microscopy, and Fourier transform infrared with attenuated total reflectance. MMT induced and stabilized the δ‐crystalline form of nylon 11. The crystal structure of nylon 11 was transformed from a hexagonal δ‐form structure to a triclinic α‐form structure during the annealing process. Meanwhile, the hydrogen bonds in the nanocomposites also exhibited some differences from neat nylon 11 after annealing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5483–5489, 2006     

Crystallization of polycaprolactone–clay nanocomposites

The isothermal crystallization process of polycaprolactone/clay nanocomposites was studied at several temperatures. The effects of the clay type (modified and unmodified) and clay content were analyzed. Bulk crystallization was studied with differential scanning calorimetry and modeled with Avrami's equation. The reinforcement phase lowered the time at which the first crystal nucleus appeared (i.e., the induction time) and fastened the global crystallization rate in comparison with that of neat polycaprolactone. The spherulitic growth was analyzed by optical microscopy with polarized light. The presence of the clay produced more and bigger spherulites in the same time and with the same undercooling degree. All these properties were strongly dependent on the polycaprolactone/clay compatibility and hence the dispersion degree achieved in the nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Crystallization behavior of polypropylene/polyamide 6/montmorillonite nanocomposites

Polymer blended materials such as polyamide 6 (PA6)/polypropylene (PP) blends have received considerable attention in recent years. To improve the compatibility of PA6 and PP, compatibilizers like maleic anhydride‐g‐polypropylene (MPP) are often added. In addition, organically modified montmorillonite (MMT) is also used to improve the properties of various materials. In this work, the crystallization behavior of PP/PA6/MMT nanocomposites with MPP compatibilizer was investigated systematically. The annealing process effectively improved the crystallization of α‐PP. The crystallization temperature (T_c) of PA6 was increased by ca 2–3 °C on introducing MPP or MMT alone to the PP/PA6 system, whereas T_c of PP underwent no obvious change. However, when MPP and MMT were added simultaneously, T_c of PP and PA6 increased by 6.6 and 4.2 °C, respectively, and a new crystallization peak corresponding to PP‐g‐PA6 copolymer phase was observed at 162.5 °C. The combined effect of MPP and MMT led to better compatibility of PP with PA6. Moreover, the results of a non‐isothermal crystallization kinetics experiment revealed that the simultaneous introduction of MPP and MMT markedly shortened the crystallization time. Copyright © 2010 Society of Chemical Industry     

Effects of swelling agents on the crystallization behavior and mechanical properties of polyamide 6/clay nanocomposites

Montomorillonite was organically modified with three different swelling agents: n‐dodecylamine, 12‐aminolauric acid, and 1,12‐diaminodecane. These organoclays and polyamide 6 (PA6) were blended in a formic acid solution. X‐ray diffraction analysis showed that the clay still retained its layer structure in the PA6/clay nanocomposite. Consequently, these materials were intercalated nanocomposites. The effects of the swelling agent and organoclay content on the crystallization behavior of the PA6/clay nanocomposites were studied with differential scanning calorimetry. The results showed that the position and width of the exothermic peak of the PA6/clay nanocomposites were changed during the nonisothermal crystallization process. The clay behaved as a nucleating agent and enhanced the crystallization rate of PA6.The crystallinity of PA6 decreased with an increasing clay content. Different swelling agents also affected the crystallization behavior of PA6. The effects of the type and content of the swelling agent on the tensile and flexural properties of PA6/clay nanocomposites were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1686–1693, 2003     

Isothermal crystallization kinetics and melting behavior of polyamide 11/silica nanocomposites prepared by in situ melt polymerization

Polyamide 11 (PA 11)/silica nanocomposites were prepared via in situ melt polymerization by the dispersion of hydrophobic silica in 11‐aminoundecanoic acid monomer. Their isothermal crystallization process and melting behaviors were analyzed by differential scanning calorimetry. The isothermal crystallization kinetics was analyzed by the Avrami equation. The obtained data showed that the model of nucleation and growth of PA 11 was not affected after the incorporation of silica and was a mixture with two‐dimensional, circular, three‐dimensional growth with thermal nucleation. Double and single melting peaks were observed depending on the crystallization temperature. The equilibrium melting point of samples was evaluated, and the spherulites growth kinetics parameters and fold surface free energy were further calculated according to the classical theories. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PA6/粘土纳米复合材料的流变性能

采用毛细管流变仪测定了原位聚合的 PA6/粘土纳米复合材料及 PA6的流变性能。结果表明 :在实验条件下 ,纳米 PA6属于假塑性流体 ,其非牛顿指数小于 PA6。在 2 40℃时 ,当剪切速率大于660 s-1时 ,纳米 PA 6的表观粘度小于 PA6,且随粘土含量的增加而逐渐降低。当剪切速率小于 932 s-1时 ,纳米 PA6的粘流活化能大于 PA6,说明纳米 PA6对温度更敏感     

粘土橡胶纳米复合材料研究进展

简要概述了粘土的有机改性机理、橡胶/粘土纳米复合材料的制备方法、结构与表征和橡胶/粘土纳米复合材料的研究进展.     

Crystal morphology and crystallization kinetics of polyamide‐11/clay nanocomposites

Polyamide‐11 (PA11)/clay nanocomposites were prepared by in situ intercalative polymerization. The crystal morphology and crystallization kinetics of these nanocomposites were investigated via polarized light microscopy (PLM), small‐angle laser scattering (SALS) and differential scanning calorimetry (DSC). PA‐11 can crystallize into well‐formed spherulites, while only very tiny crystallites were observed by PLM and SALS for the nanocomposites. Both isothermal and non‐isothermal crystallization methods were employed to investigate the crystallization kinetics by DSC. Both techniques showed an increased crystallization rate with the addition of clay. However, the Avrami exponent decreased with the addition of clay in isothermal crystallization but showed a wide range of values depending on the cooling rate in the non‐isothermal crystallization. The changes in crystal morphology and crystallization kinetics can be understood as being due to the ‘supernucleating’ effect of the nanodispersed clay layers. Copyright © 2004 Society of Chemical Industry     

Crystallization behavior of PA‐6 clay nanocomposite hybrid

Polyamide‐6 (PA‐6)/clay (modified montmorillonite) hybrid was synthesized by melt blending at high shear stress. ²⁷Al‐NMR of solid state shows that the clay is not modified after melt blending. Using wide‐line ¹H‐NMR and TEM, it is demonstrated that the nanocomposite exhibits mainly an exfoliated structure. It is shown that the modified montmorillonite induces the crystallization of PA‐6 predominantly in γ‐form. The presence of clay in PA‐6 increases the polymer crystallization temperature, and decreases its melting point. These phenomena show that a certain number of interactions develop near the reinforcing material, and that the latter plays a particular role of nucleating agent. However, the crystallization is not spherulitic and the assumption of macromolecular orientation in the vicinity of the clay is demonstrated by the observations carried out in DSC and AFM. These particular properties of orientation will have a particular importance on the mechanical behavior of the nanocomposite material. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2416–2423, 2002     

Synthesis and characterization of nylon 6/clay nanocomposites prepared by ultrasonication and in situ polymerization

Nylon 6 nanocomposites were prepared by the in situ polymerization of ε‐caprolactam with ultrasonically dispersed organically modified montmorillonite clay (Cloisite 30B®). Dispersions of the clay platelets with concentrations in the range 1–5 wt % in the monomer were characterized using rheological measurements. All mixtures exhibited shear‐thinning, signifying that the clay particles were dispersed as platelets and forming a “house of cards” structure. Samples with Cloisite concentrations above 2 wt % showed a drop in viscosity between the initial shearing and repeated shearing, indicative of shearing breaking down the initial “house of cards” structures formed on sonication. DMTA measurements of the samples showed an increase in the β‐relaxation temperature with increasing clay concentration. The bending modulus, at temperatures below T_g, showed an increase with increasing clay concentration up to 4 wt %. X‐ray diffraction measurements showed that all nylon 6/Cloisite 30B samples were exfoliated apart from the 5 wt %, which showed that some intercalated material was present. The nylon crystallized into the α‐crystalline phase, which is the most thermodynamically stable form. Preference for this form may be a consequence of the long time associated with the postcondensation step in the synthesis or the influence of the platelets on the nucleation step of the crystal growth. DSC measurements showed a retardation of the crystallization rate of nanocomposite samples when compared with that of pure nylon 6, due to the exfoliated clay platelets hindering chain movement. This behavior is different from that observed for the melt‐mixed nylon 6/clay nanocomposites, which show an enhancement in the crystallization rate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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 behavior of syndiotactic polystyrene nanocomposites for melt‐ and cold‐crystallizations

Analyses of the effects of montmorillonite (clay) on the crystallinity and crystallization behavior of syndiotactic polystyrene (s‐PS) were investigated by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The dispersibility of the clay in s‐PS nanocomposites was studied by X‐ray and transmission electron microscopy (TEM). The clay was dispersed into the s‐PS matrix by melt blending on a scale of 1–2 nm or few tenths–100 nm, depending on the surfactant treatment. On adding clay, the crystallization behavior of the s‐PS tends to convert into the β‐crystal from the α‐crystal after being cold‐crystallized because the clay plays a vital role in facilitating the formation of the thermodynamically favored β‐form crystal when the s‐PS is cold‐ or melt‐crystallized. This phenomenon leads to a change in a conventional mechanism of molecular packing for the s‐PS. Evidently, the clay significantly affects the crystallinity and crystallization behavior of the s‐PS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2492–2501, 2002     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

Silicate layer dispersion in copolymer/clay nanocomposites

Factors of silicate layer dispersions in polymers have been studied with copolymers. The influence of the copolymerization ratio of copolymers and the alkyl chain lengths of organomodified reagents of organophilic clay has been examined. The dispersion of silicate layers in copolymers is dependent on the copolymerization ratios of the functional groups, that is, the polarity of the polymer matrix. The alkyl chain lengths of organomodified reagents also have an important influence on silicate layer dispersions. From a comprehensive viewpoint, the polarity matching between polymers and organophilic clay is an important factor for silicate layer dispersions in polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1554–1557, 2005     

尼龙6/粘土纳米复合材料的性能

对尼龙6/粘土纳米复合材料(PA6CN)的力学性能、结晶性能、流变性能、热稳定性、阻隔性能、阻燃性能、各向异性和可纺性进行了综述。加入粘土后,基体尼龙6的晶型变为γ型,改善了尼龙6的力学性能,提高了热变形温度,降低了吸水率,改善了气体阻隔性和材料的阻燃性,拓宽了复合材料的应用范围。     

Crystallization and melting behavior of iPP studied by DSC

This article is a part of a study of model and bulk composites, based on isotactic polypropylene (i-PP) and glass (or carbon) fibers, produced from knitted textile preforms of hybrid yarns. First, we report the results on crystallization and fusion of textile-grade i-PP, used for the processing of hybrid yarns and the corresponding knitted fabrics. The kinetics of the crystallization process, in the dynamic and isothermal regime, was followed by DSC, and the results were analyzed by Avrami, Ozawa, and Harnisch-Muschik methods. Isothermal crystallization of i-PP was carried out at 388–400 K, and values for the Avrami exponent ranging from 1.93 to 4.39 were determined. The equilibrium melting temperature was determined by the Hoffman-Weeks method, and γ = 2.54 was found. Double melting peaks were observed both when the crystallization was performed at lower temperatures (isothermal regime) and at higher cooling rates (nonisothermal regime). A single melting peak appeared upon melting following isothermal crystallization at 400 K. The nonisothermal kinetics data showed that the peak crystallization temperature changes from 377 to 386 K as the cooling rate decreases from 20 to 3 K/min. Applying the Ozawa method, a value of the exponent n = 2.33 was determined, which is in agreement with the results for isothermal crystallization at 391–400 K. The Harnisch-Muschik approach was also applied to compare the results for n, and a similar trend in the results of isothermal and nonisothermal crystallization was found, due to the predominant homogeneous mechanism of nucleation at lower cooling rates (lower isothermal T_c) in spite of being heterogeneous at higher cooling rates (higher isothermal T_c). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 395–404, 1998