Nonisothermal crystallization kinetics of polyoxymethylene/montmorillonite nanocomposite

The nonisothermal crystallization kinetics of polyoxymethylene (POM), polyoxymethylene/Na–montmorillonite (POM/Na–MMT), and polyoxymethylene/organic–montmorillonite (POM/organ–MMT) nanocomposites were investigated by differential scanning calorimetry at various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of POM/Na–MMT and POM/organ–MMT nanocomposites. The difference in the values of the exponent n between POM and POM/montmorillonite nanocomposites suggests that the nonisothermal crystallization of POM/Na–MMT and POM/organ–MMT nanocomposites corresponds to a tridimensional growth with heterogeneous nucleation. The values of half‐time and the parameter Z_c, which characterizes the kinetics of nonisothermal crystallization, show that the crystallization rate of either POM/Na–MMT or POM/organ–MMT nanocomposite is faster than that of virgin POM at a given cooling rate. The activation energies were evaluated by the Kissinger method and were 387.0, 330.3, and 328.6 kJ/mol for the nonisothermal crystallization of POM, POM/Na–MMT nanocomposite, and POM/organ–MMT nanocomposite, respectively. POM/montmorillonite nanocomposite can be as easily fabricated as the original polyoxymethylene, considering that the addition of montmorillonite, either Na–montmorillonite or organ–montmorillonite, may accelerate the overall nonisothermal crystallization process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2281–2289, 2001     

聚丙烯／蒙脱土纳米复合材料的制备与性能

用烷基季铵盐对钠基蒙脱土进行有机化处理,使其成为有机蒙脱土。X射线衍射（XRD）表明有机阳离子已同钠离子发生离子交换作用,导致层间距扩大。用熔融插层法制备聚丙烯／蒙脱土纳米复合材料,测试了力学性能。通过XRD、DSC等手段研究了其结构与结晶行为,并与聚丙烯进行了对比。实验表明,通过熔融插层可使聚丙烯插层于蒙脱土片层之中,且所得聚合物的冲击强度有所提高。     

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     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

乳液插层法天然橡胶/蒙脱土纳米复合材料的制备及其性能

采用乳液插层法制备了天然橡胶/蒙脱土（NR/MMT）纳米复合材料,采用透射电子显微镜（TEM）研究了复合材料的亚微观形态,并对复合材料的力学性能和耐磨耗性能进行了研究。TEM结果显示,MMT片层以纳米尺寸均匀分散在NR基体中;力学性能测试结果表明,当MMT用量小于12份时,纳米复合材料的力学性能随MMT用量的增加而逐渐增大,NR/MMT纳米复合材料具有优良的力学性能;蒙脱土的加入稍微降低纳米复合材料的耐磨性。     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Crystallization and thermoelectric behavior of conductive-filler-filled poly(ε-caprolactone)/poly(vinyl butyral)/montmorillonite nanocomposites

Crystallization and thermoelectric properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB)/montmorillonite (MMT) nanocomposites containing carbon black (CB) have been studied as a functions of a small amount of amorphous PVB content and a wide range of molecular weight of PVB. X-ray diffraction data of PCL/PVB/MMT nanocomposites indicates most of the swellable silicate layers are exfoliated and randomly dispersed into PCL/PVB system. The band spacings of PCL spherulites in PCL/PVB/MMT nanocomposites decrease with increasing PVB content, and this indicates that increasing the PVB content greatly shortens the period of lamellar twisting. The presence of 1 wt% MMT and higher molecular weight of PVB also shorten the period of PCL lamellar twisting. Nucleation and crystallization parameters, such as growth rate G and Avrami exponent n, can be determined by using POM and DSC isothermally crystallized at 41 °C. For samples with the same CB content, the intensity of positive temperature coefficient (PTC) (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the nanocomposites was increased as the content and the molecular weight of PVB increases. The change of the PTC property related to the morphological difference (i.e. period of lamellar twisting) in the nanocomposites can be discussed.     

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。     

Preparation and properties of polypropylene/montmorillonite layered nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites have been prepared by melt intercalation using organomontmorillonite and conventional twin screw extrusion. The dispersibility of silicate layers of the montmorillonite in the composites was investigated by using X‐ray diffractometer and transmission electron microscopy (TEM). The silicate layers of montmorillonite are dispersed at the nanometer level in the PP matrix, as revealed by X‐ray and TEM results. The tensile strength of PP/MMT is not much improved compared with pure PP or conventional filled composites. However, the impact strength is greatly improved at lower content of MMT. © 2000 Society of Chemical Industry     

Study on the Crystallization Properties of Polypropylene/Montmorillonite Composites

The crystalline size of polypropylene (PP) filled with montmorillonite (MMT) was studied by X-ray diffraction (XRD). The isothermal crystallization behavior of polypropylene was studied by means of differential scanning calorimetry (DSC). The Avrami equation was used to describe the isothermal crystalline kinetics of PP/MMT composites. The result showed that the addition of MMT decreased the crystalline size L _hkl of the polymer. MMT was used as nucleating agent during isothermal crystallization process of polypropylene. The addition of montmorillonite decreased the crystallization time of the polypropylene and the melt point was raised. The value of Avrami exponent n was related with the crystallization temperature. The value of Avrami pre-index factor k of PP/MMT composite was decreased with increasing crystallization temperature. The value of half crystallization time t _1/2 of PP/MMT composite was less than that of PP at a given crystallization temperature, signifying that montmorillonite acted as nucleating agent, accelerated the overall crystallization process.     

两步法制备剥离型聚丙烯/蒙脱土纳米复合材料(Ⅱ)熔融行为及流变性能

采用DSC及XRD研究了聚丙烯/蒙脱土纳米复合材料(PMN)的结晶熔融行为.DSC的结果表明,复合材料熔点升高,但相对结晶度下降.XRD结果表明,蒙脱土作为成核剂促进了聚丙烯β晶型的生成;同时β晶型的增长抑制了α晶体的长大,减小了α晶粒尺寸,提高了复合材料的力学性能.系统研究了复合材料的流变性能,探讨了蒙脱土含量、温度、剪切速率等因素对复合材料黏度特性的影响,结果表明,复合体系总体上呈现剪切变稀的特性,体系表观剪切黏度随蒙脱土含量的升高逐渐下降,材料加工性能优于聚丙烯基体.     

Effective preparation and characterization of montmorillonite/poly(ε‐caprolactone)‐based polyurethane nanocomposites

In this study, montmorillonite (MMT)/poly(?‐caprolactone)‐based polyurethane cationomer (MMT/PCL‐PUC) nanocomposites were prepared and their mechanical properties, thermal stability, and biodegradability were investigated. PCL‐PUC has 3 mol % of quaternary ammonium groups in the main chain. The MMT was successfully exfoliated and well dispersed in the PCL‐PUC matrix for up to 7 wt % of MMT. The 3 mol % of quaternary ammonium groups facilitated exfoliation of MMT. The 1 wt % MMT/PCL‐PUC nanocomposites showed enhanced tensile properties relative to the pure PCL‐PU. As the MMT content increased in the MMT/PCL‐PUC nanocomposites, the degree of microphase separation of PCL‐PUC decreased because of the strong interactions between the PCL‐PUC chains and the exfoliated MMT layers. This resulted in an increase in the Young's modulus and a decrease in the elongation at break and maximum stress of the MMT/PCL‐PUC nanocomposites. Biodegradability of the MMT/PCL‐PUC nanocomposites was dramatically increased with increasing content of MMT, likely because of the less phase‐separated morphology of MMT/PCL‐PUC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The Effect of Spray-Freeze Drying of Montmorillonite on the Morphology,Dispersion, and Crystallization in Polypropylene Nanocomposites

The spray-freeze drying (SFD) technique was applied to sonicated aqueous suspensions of spray-dried montmorillonite clay (MMT) to produce highly porous agglomerates (SFD-MMT). Both MMT (used as a reference) and SFD-MMT were subsequently incorporated in polypropylene (PP) via melt compounding to produce 2 wt % nanocomposites with and without maleic anhydride grafted polypropylene (PP-g-MA). Polypropylene nanocomposites containing SFD-MMT exhibited thinner silicate flake layers compared to large agglomerates in PP/MMT nanocomposites. SFD-MMT particles became even more finer in the presence of PP-g-MA (i.e., in PP/PP-g-MA /SFD-MMT) where it hindered PP crystallization instead of serving as nucleation sites for the PP crystallization during rapid cooling. SFD-MMT improved the thermal stability of PP/PP-g-MA by 30°C compared to only 5–8°C for MMT/nanocomposites. MMT acts as a heterogeneous nucleating agent in the nucleation-controlled PP nanocomposites, but the hindrance effect was observed for the PP/PP-g-MA with SFD-MMT. PP/PP-g-MA/SFD-MMT exhibited twice the edge surface energy as compared to PP/PP-g-MA/MMT. The incorporation of both types of MMT raised the tensile moduli of PP and PP/PP-g-MA, with no improvement in their tensile strength and a decrease in the elongation at break. The PP/PP-g-MA/SFD-MMT showed brittle failure. POLYM. ENG. SCI., 60:168–179, 2020. © 2019 Society of Plastics Engineers     

含氮相容剂对聚丙烯/蒙脱土复合材料阻燃性能的影响

以N-羟甲基丙烯酰胺接枝聚丙烯(PP-g-NHA)为相容剂,采用熔融插层法,制备聚丙烯(PP)/蒙脱土(MMT)纳米复合材料;采用X射线衍射仪(XRD)、偏光显微镜(POM)、差式扫描量热仪(DSC)和氧指数仪(LOI)等对复合材料的微观结构和性能进行了研究。结果表明PP-g-NHA能有效地改善PP与MMT的相容性,当蒙脱土用量为5%、PP-g-NHA用量为15%时,PP/PP-g-NHA/MMT纳米复合材料的极限氧指数(LOI)由PP的18提高到23。X射线衍射(XRD)测试表明,PP已经插层进入到蒙脱土片层中,当蒙脱土用量为5%、PP-g-NHA用量为5%时插层效果最好,DSC分析结果表明,复合材料的熔融温度和分解温度都有所上升。     

Crystallization behavior of polymer/montmorillonite nanocomposites. Part III. Polyamide-6/montmorillonite nanocomposites, influence of matrix molecular weight, and of montmorillonite type and concentration

Several series of polyamide-6 (PA-6) nanocomposites, differing in montmorillonite (MMT) type and content and PA-6 matrix molecular weight, were prepared by melt-extrusion and the associated PA-6 crystallization behavior and morphology was evaluated using (synchrotron) X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. The nucleating ability of silicate layers is poor in PA-6 nanocomposites made by melt-extrusion because highly active, stable PA-6 crystallization precursors are generated during melt-extrusion. In most of the studied PA-6/MMT nanocomposites the dispersed silicate layers act as impurities and decrease rather than increase the overall crystallization kinetics of PA-6, especially at high MMT contents. Furthermore, at a given MMT concentration, the crystal growth retardation inflates with increasing degree of exfoliation, which dependents on the MMT type and which increases with increasing PA-6 molecular weight. One of the considered MMT types leads to a poorly exfoliated nanomorphology and as a result no retardation of crystal growth is observed. Furthermore, the disturbed crystal growth does not alter the PA-6 semicrystalline stack morphology. Moderate nucleation effects due to the presence of MMT can be observed when the particle load is low (low amount of MMT and/or poor degree of exfoliation) and provided the supercooling is sufficiently large.     

SBS nanocomposites as toughening agent for polypropylene

The toughening of polypropylene [PP] with styrene–butadiene–styrene rubber [SBS]/montmorillonite [MMT] nanocomposites was investigated with respect to morphological, thermal, and mechanical properties. The MMT/SBS nanocomposites were prepared in an internal mixer, using an epoxidized SBS [SBSe] to investigate its effect as a compatibilizer. The MMT/SBS nanocomposite was added to PP up to 10 wt%, aiming at material toughening. Transmission electron microscopy (TEM) revealed MMT induced dispersed-phase reductions when compared to typical PP/SBS blends. In addition, changes in the PP crystallization process were observed in the presence of the nanocomposite. Surprisingly, the use of nanofiller, combined with SBSe compatibilizer agent, increased the PP impact strength by about 60%, with no reduction in the tensile module.     

聚丙烯/蒙脱土纳米复合材料的制备和性能

采用熔融插层法在双螺杆挤出机中制备了聚丙烯(PP)/蒙脱土(MMT)纳米复合材料,纳米复合材料机械性能测试结果表明,当有机MMT质量分数为2%时,复合材料的弯曲强度明显优于PP。扫描电镜观测不到纳米复合材料中明显的有机-无机相畴,表明MMT片层分散均匀,分散尺度已基本达到纳米级。DSC(差示扫描量热仪)分析测试结果表明,MMT的加入提高了PP的结晶速率,并使结晶度增大。     

聚丙烯/蒙脱土纳米复合材料的制备与性能

合成了TiCl4/MgCl2/MMT插层催化剂,通过原位聚合制备了聚丙烯/蒙脱土纳米复合材料。X射线衍射结果表明:蒙脱土在聚丙烯基质中达到了纳米级分散。与纯聚丙烯(PP5004)相比,聚丙烯/蒙脱土纳米复合材料的力学性能、维卡软化点、热变形温度以及热分解温度都有所提高。     

PTT/MMT纳米复合材料的研究

采用熔融共混的方法制备了聚对苯二甲酸丙二醇酯/有机蒙脱土（PTT/MMT）纳米复合材料,通过DSC、热台偏光显微镜等研究了PTT/MMT纳米复合材料的结晶行为,测定了纳米复合材料的力学性能,并用熔体流变仪研究了PTT/MMT纳米复合材料熔体流变性能。结果表明：随着PTT/MMT纳米复合材料中蒙脱上含量的增加,PTT/MMT纳米复合材料的熔融结晶温度增高,纳米复合材料的力学性能有一定的提高;PTT-蒙脱土纳米复合材料熔体的流变性能随MMT含量的增加非牛顿性减弱,熔体的粘流活化能减小。