Studies on the Nonisothermal Crystallization Behavior of Polypropylene/Multiwalled Carbon Nanotubes Nanocomposites

Polypropylene/multiwalled carbon nanotubes (PP/MWNTs) nanocomposites were prepared by a melt compounding process. The morphology and nonisothermal crystallization of these nanocomposites were investigated by means of optical microscopy, scanning electron microscopy, and differential scanning calorimetry. Scanning electron microscope micrographs of PP/MWNTs composite showed that the MWNTs were well dispersed in the PP matrix and displayed a clear nucleating effect on PP crystallization. Avrami theory, modified by Jeziorny and Mo's method, was used to analyze the kinetics of the nonisothermal crystallization process. It was found that the addition of MWNTs improved the crystallization rate and increased the peak crystallization temperature of the PP/MWNTs nanocomposites as compared with PP. The results show that the Jeziorny theory and Mo's method successfully describe the nonisothermal crystallization process of PP and PP/MWNTs nanocomposites.     

Effects of Montmorillonite on the Nonisothermal Crystallization Behavior of the Poly(trimethylene terephthalate)/Polypropylene/Montmorillonite Nanocomposites

Organic montmorillonite (MMT) reinforced poly(trimethylene terephthalate) (PTT)/ polypropylene (PP) nanocomposites were prepared by melt blending. The effects of MMT on the nonisothermal crystallization of the matrix polymers were investigated using differential scanning colorimetry (DSC) and analyzed by the Avrami equation. The DSC results indicated that the effects of MMT on the crystallization processes of the two polymers exhibited great disparity. The PTT's crystallization was accelerated significantly by MMT no matter whether PTT was the continuous phase or not, but the thermal nucleation mode and three-dimensional growth mechanism remained unchanged. However, in the presence of MMT, the PP's crystallization was slightly retarded with PP as the dispersed phase, and was influenced little with PTT as the dispersed phase. When the MMT content was increased from 2_wt% to 7_wt%, the crystallization of the PTT phase was slightly accelerated, whereas the crystallization of the PP phase was severely retarded, especially at lower temperatures. Moreover, the nucleation mechanism for the PP's crystallization changed from a thermal mode to an athermal one. In the polypropylene-graft-maleic anhydride (PP-g-MAH) compatibilized PTT/PP blends, with the addition of 2_wt% MMT during melt blending, the T _c (PTT) shifted 7.8°C to lower temperature and had a broadened exotherm, whereas the T _c (PP) shifted 17.1°C to higher temperature, with a narrowed exotherm. TEM analysis confirmed that part of the PP-g-MAH was combined with MMT during blending.     

Nonisothermal Crystallization Behavior of Polypropylene-C60 Nanocomposites

The nonisothermal crystallization behavior of polypropylene (PP) and PP-fullerene (C₆₀) nanocomposites was studied by differential scanning calorimetry (DSC). The kinetic models based on the Jeziorny, Ozawa, and Mo methods were used to analyze the nonisothermal crystallization process. The onset crystallization temperature (T_c), half-time for the crystallization (t_1/2), kinetic parameter (F(T)) by the Mo method and activation energy (ΔE) estimated by the Kissinger method showed that C₆₀ accelerates the crystallization of PP, implying a nucleating role of C₆₀. Furthermore, due to the reduced viscosity of PP by adding 5% C₆₀, the parameters of crystallization kinetics for the PP-5%C₆₀ nanocomposites changed remarkably relative to that of neat PP and when lower contents of C₆₀ were added to PP.     

Nonisothermal Crystallization Kinetics of Nylon 66/Montmorillonite Nanocomposites

Polyamide 66(PA66)/montmorillonite nanocomposites were prepared via direct melt compounding. The nonisothermal crystallization of PA66 and PA66/MMT nanocomposites were investigated by differential scanning calorimetry. The results show that MMT platelets play a competing role in the crystallization process of nylon 66. On the one hand, they can act as a nucleator for the PA66 matrix, accelerating the crystallization rate; on the other hand, they retard the crystal/spherulite growth, especially for nanocomposites with higher MMT content. The analysis results using Jeziorny and Mo equations verify the dual actions of the nucleation and the obstruction of crystallization of MMT in the PA66 matrix. Kissinger's method was used to obtain the activation energy of the crystallization process; the results confirm that the incorporation of MMT causes the above actions.     

Influence of Hollow Glass Microspheres Modified by a Rare-Earth/Titanium Coupling Agent on the Nonisothermal Crystallization of Polypropylene

Hollow glass microspheres (HGMs) were surface modified by a rare-earth/titanium coupling agent. Then polypropylene/HGMs composites were prepared by the method of melt blending. The nonisothermal crystallization of the polypropylene (PP) and its composites were investigated by differential scanning calorimetry. The results showed the modified HGMs caused a decrease in the peak crystallization temperature and onset crystallization temperature. Further analysis of the nonisothermal crystallization kinetics, by using the Jeziorny and Mo equations, showed that the crystallization rate rose with increasing cooling rate. Moreover, the presence of the modified HGMs slightly increased the crystallization rates of PP.     

Quantitative characterization of the orientation of macromolecules in intercalated nanocomposites of polyolefins/layered silicates by Raman spectroscopy

Raman spectroscopy is used to study variations in the orientational order of macromolecules in the uniaxially drawn intercalated nanocomposites based on two polymer matrices (polyethylene (PE) and isotactic polypropylene (PP)) and a filler (modified clay (MC)). The orientation parameters of macromolecules measured using Raman spectroscopy are compared with the X-ray data. It is demonstrated that, for the uniaxially drawn PE-MC and PP-MC intercalated nanocomposites, the filler impedes the orientation along the draw direction for the macromolecules localized in the noncrystalline phase of the polymer matrix. The orientational ability of the PE and PP crystallites in nanocomposites is not affected by the filler.     

Nonisothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer with Poly(oxypropylene)diamine Intercalated Montmorrilonite

Films of ethylene vinyl alcohol copolymer (EVOH) and EVOH containing poly(oxypropylene)diamine intercalated montmorrilonite were prepared by solution casting. The nanostructures and viscosity were characterized by small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and rheological testing. The nonisothermal crystallization kinetics of the samples were investigated by the Ozawa's and Mo's methods and the crystallization activation energy by Kissinger's model. The SAXS and TEM analysis demonstrated that the nanoplatelets, with an intercalated structure, were dispersed in the EVOH matrix. The rheological tests showed that the incorporation of the modified clay could increase the viscosity of the composite system. The Mo's method more successfully described the nonisothermal ctystallization behavior of neat EVOH and its nanocomposites as compared with the Ozawa's method. Adding the nanoclays had a heterogeneous nucleation effect to accelerate the crystallization of EVOH despite hindering the macromolecular chains movement.     

Influences of Carbon Nanotube Networking on the Conductive,Crystallization, and Thermal Expansion Behaviors of PA610-Based Nanocomposites

The electrical, crystallization and thermal expansion behaviors of polyamide 610 (PA610)/multi-walled carbon nanotube (CNT) nanocomposites prepared by melt mixing were investigated. Electron microscopy (Scanning Electron Microscopy and Transmission Electron Microscopy) revealed that a good dispersion of CNT and CNT network was obtained in the PA610 matrix. Addition of CNT to PA610 matrix led to polymer nanocomposites exhibiting higher electrical conductivity and lower thermal expansion. The network of CNT in the PA610 matrix, which can be tuned by the loading of CNT and the melt isothermal treatment, was found to play an important role in reducing thermal expansion and achieving higher conductivity. Furthermore, it was shown that significant reduction in thermal expansion in PA610/CNT nanocomposites was due to both thermally insensitive CNT and formation of CNT network.     

Melting and Crystallization Behaviors of Poly(Lactic Acid) Modified with Graphene Acting as a Nucleating Agent

Graphene (GN)-filled polylactic acid (PLA) nanocomposites were prepared through a solution blending method with GN weight percent ranging from 0.5 to 2?wt%. Rheological, melting and crystallization behaviors of the prepared PLA/GN nanocomposites were investigated by means of dynamic rheological measurements and differential scanning calorimetry (DSC). The shear viscosities of the PLA/GN nanocomposites decreased with increasing GN content, which was remarkably different from previous reports on the modifications using traditional nanofillers (e.g., clay, carbon nanotubes, etc.). The nonisothermal melt crystallization kinetic analysis suggested that GN served as a nucleating agent and could considerably promote the PLA’s crystallization through heterogeneous nucleation. Our findings suggested that at relatively low cooling rates (??≤?10?°C/min) even a small amount of GN promoted the nucleation and considerably increased the crystallization rate. However, the crystallinity began to decrease at higher cooling rates (e.g., ??≥?20?°C/min), especially when the GN content was high (e.g., 2?wt%), possibly owing to the GN aggregation effect considering PLA is a slowly crystallizing polymer.     

Nonisothermal Crystallization Kinetics of Poly(ϵ-caprolactone)/Zinc Oxide Nanocomposites with High Zinc Oxide Content

Poly(?-caprolactone) (PCL)/zinc oxide (ZnO) nanocomposites (PCLZs) with high ZnO contents were prepared by using ZnO to initiate ring-opening polymerization of ?-caprolactone (?-CL). The Ozawa and Mo equations were chosen to analyze the nonisothermal crystallization kinetics of PCLZs. The results showed that the Ozawa equation was not successful while the Mo equation was successful in describing the nonisothermal crystallization kinetics of PCLZs. When the ZnO content in PCLZs was high, the effect of ZnO content on crystallization behaviors was small and the crystallization rates of PCLZs only increased slightly with the increase of ZnO content. Crystallization activation energies (E_c s) of PCLZs were estimated by Kissinger's method. The results showed that the E_c s of PCLZs with three different ZnO contents were nearly identical within the tolerance, which further demonstrated that the effect of ZnO content on crystallization behaviors was small when the ZnO content in PCLZs was high.     

Synthesis of Polypropylene/Attapulgite Nanocomposites and Their Crystallization Behavior Studied by Step-Scan DSC

Attapulgite (AT) was modified by grafting with butyl acrylate (BA) via polymerizations initiated by Gamma radiation. Polypropylene (PP)/AT nanocomposites were synthesized via melt extrusion in a twin-screw extruder. Fourier transform infrared (FTIR) spectroscopy and thermogravimetry (TG) were used to assess the structure of the hybrid materials and the dispersion of AT was verified by transmission electron microscopy (TEM). The crystallization kinetics of PP/AT nanocomposites were investigated by differential scanning calorimetry (DSC) and analyzed by using the Avrami method. The isothermal crystallization kinetics showed that the addition of AT increased both the crystallization rate and the isothermal Avrami exponent of PP. Step-scan differential scanning calorimetry (SDSC) was used to study the influence of AT on the crystallization and subsequent melting behavior. The results revealed that PP and PP/AT nanocomposites experienced multiple melting and secondary crystallization processes during heating. The melting behaviors of PP and PP/AT nanocomposites varied with the variation of crystallization temperature and AT content.     

Synthesis and Thermal Behavior of Silica‐Graft‐Polypropylene Nanocomposites Studied by Step‐Scan DSC and TGA

Silica graft poly(propylene) (silica‐g‐PP) nanocomposites were successfully prepared by radical grafting copolymerization and ring‐opening reaction. Their thermal properties were studied by step‐scan differential scanning calorimetry (SDSC) and thermogravimetric analysis (TGA). The exothermic peaks in the IsoK baseline (C_p,IsoK, nonreversing signal) of SDSC reveal that PP and silica‐g‐PP nanocomposites undergo melting‐recrystallization‐remelting during heating. The peak temperatures of recrystallization and remelting shift upward with the existence of nanoparticles in the PP matrix. The thermal degradation kinetics of silica‐g‐PP nanocomposites were investigated using nonisothermal TGA and the Flynn‐Wall‐Ozawa method. The results indicate that the thermal stability was significantly improved with increasing silica content, mainly because of the physical‐chemical adsorption of the volatile degradation products on the nanoparticles that delays their volatilization during decomposition, and the covalent interaction between nanoparticles and PP chains, which will also reduce the breakage of PP backbone chains.     

Effect of Spherical Nanoparticles on the Motion of Macromolecular Chains and Segments of Isotactic Polypropylene. I. Dynamic Mechanical and Thermal Properties

The role of spherical nano-CaCO₃ particles treated with 2 wt% and 6 wt% stearic acid (SA), respectively, on the motion of macromolecular chains and segments of isotactic polypropylene (iPP) was studied through the dynamic mechanical analysis and nonisothermal crystallization. Higher nucleation activity of the particles and more nucleating sites were achieved in the 6 wt% SA treated particle nanocomposites with respect to the 2 wt% SA counterpart. The increased nucleation efficiency caused high inhomogeneity and thus large mobility of the amorphous phase of iPP, which favored a low glass transition temperature (T_g ) in the nanocomposites. However, the spherical nanoparicles also spatially restrained the motion of macromolecular chains and segments, and the better the nanoparticles dispersed, the stronger the restriction was. Thus the glass transition temperature (T_g ) of the nanocomposites decreased with increasing filler loading but recovered at a certain particle concentration. At this filler content, the maximal α-transition temperature (T_α ) and the main melting peak temperature (T_m1 ) as well as the lowest degree of crystallinity (X_PP ) also occurred. This critical filler loading appeared at lower value (20 wt%) in 6 wt% SA treated nano-CaCO₃ composites with respect to 2 wt% SA counterpart (25%) due to the better dispersion of particles in the former. It was concluded that the mobility of the macromolecular chains and segments of iPP was dominated by the competition of the spatial confinement and nucleation effect of nano-CaCO₃ particles in the matrix.     

非晶一次晶化过程微观组织演化和生长动力学的相场法研究

在晶化物理模型中添加扩散系数对晶化过程的影响, 采用相场方法研究初始形核率和初始形核半径对一次晶化过程中微观组织和生长动力学的影响。结果表明: 随着初始形核率的增加, 相同时间内非晶一次晶化的晶粒数量逐渐增加, 晶粒尺寸逐渐减小。晶化分数随着演化时间和初始形核率的增加逐渐增大, 初始形核率越大, 相同演化时间内的晶化分数越高。不同初始形核半径情况下, 非晶一次晶化过程中的晶粒数量和尺寸随着演化时间的增加基本保持不变。晶化分数随着演化时间的增加而增大。不同初始形核率和初始形核半径情况下所对应的生长指数均小于1, 表明初始形核率和初始形核半径对晶化方式无影响, 均为一次晶化。改变初始形核率和初始形核半径可调控一次晶化微观组织结构, 而晶粒尺寸及晶化分数直接关系到合金性能。     

A Kinetic Study on the Thermal Degradation of Polypropylene/Attapulgite Nanocomposites

In this work, a polypropylene (PP)/attapulgite nanocomposite was prepared via melt blending using a novel organically modified attapulgite (OATP). The thermal stability of PP/clay nanocomposites compared to pure PP was examined in nitrogen using a kinetic analysis. The kinetic parameters, including reaction order and activation energy (A and E _a) of the degradation process were determined by applying the Flynn‐Wall‐Ozawa method using derivative thermogravimetric (DTG) curves. At the same time, the effect of organic attapulgite on thermal decomposition of polypropylene matrix was analyzed. As a result, PP/OATP nanocomposites have slightly higher degradation temperature than that of the pure PP. The values of the reaction order of PP and PP/OATP nanocomposites are close to 1 in the nonisothermal degradation process. The activation energies of PP/OATP nanocomposites also increase slightly compared to the pure PP, thus it is suggested that the org‐attapulgite has little effect on the thermal stability of the pure PP.     

Nonisothermal Crystallization Behavior of Polypropylene Grafted Silane and Styrene Using γ-Ray Irradiation

Polypropylene grafted silane and styrene (named PP-g-Si/St in this article) was successfully prepared by radical graft polymerization initiated by γ-ray irradiation. The influence of total absorbed dose on the graft ratio of vinyltrimethoxysilane onto PP and the melt flow rate (MFR) of the PP-g-Si/St product were studied. The effect of graft ratios of vinyltrimethoxysilane on the melting point and nonisothermal crystallization kinetics of PP-g-Si/St was investigated by the method of differential scanning calorimetry (DSC). With increasing vinyltrimethoxysilane and styrene (used as viscosity modifier and free radical source) grafted on PP, the melting point of PP-g-Si/St became lower. Several different analysis methods, including those of Avrami, Jeziorny, and Mo and colleagues, were employed to describe the nonisothermal crystallization process of the grafted samples. The results indicate that the peak temperature of crystallization of PP-g-Si/St sample was lower than that of virgin PP. Crystallization kinetics revealed that the rates of nucleation and growth were affected differently by the graft ratio of vinyltrimethoxysilane onto PP. The activation energy was calculated on the basis of the method of Kissinger, and the values were 253.6 and 215.7 kJ/mol for virgin PP and PP-g-Si/St, respectively.     

Study of the Nonisothermal Crystallization Kinetics and Melting Behaviors of Polypropylene Reinforced with Single-Walled Carbon Nanotubes Nanocomposite

Nonisothermal crystallization kinetics of polypropylene (PP) nanocomposite reinforced with 0.5 wt. % single-walled carbon nanotubes (SWNT) was characterized by differential scanning calorimetry at five different cooling and heating rates. The Avrami, Ozawa, and Seo-Kim kinetic models were used to describe the nonisothermal crystallization of the polymer and its nanocomposite. The addition of nano-filler, in general, improved the crystallization rate and increased the peak crystallization temperature of the nanocomposite as compared to PP. The results show that the Avrami and Seo-Kim models are suitable under different cooling rate conditions but that the Ozawa model is inappropriate for the nanocomposite. Equilibrium melting temperatures, derived from the linear Hoffman-Weeks equation, were shown to decrease in the nanocomposite. Additional analysis was performed based on the Thomson-Gibbs, Lauritzen-Hoffman, and Dobreva-Gutzowa theories, which were applied to take into account the lamellar thickness, nucleating agent, and nucleating activity of the nanocomposite in the nonisothermal melt crystallization process.     

Micromechanical properties of poly(butylene terephthalate) nanocomposites with single- and multi-walled carbon nanotubes

Polymer nanocomposites with carbon nanotubes (CNT) are becoming important structural materials because of their superior mechanical properties and easy processability. The objective of the work is to investigate the influence of small amounts of single walled carbon nanotubes (SWCNT), as well as multi-walled carbon nanotubes (MWCNT), on the microhardness of a thermoplastic polymer such as poly(butylene terephthalate) (PBT). The nanocomposites were obtained by introducing the CNT into the reaction mixture during the synthesis of PBT. The polymers without carbon nanotubes (reference material) and with carbon nanotubes were synthesized using an in-situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of the single walled and from 0.01 to 0.35 wt% of the multi-walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and by ultra high speed stirring. The nanocomposites were extruded followed by injection molding. The samples were characterized by electron microscopy and microindentation hardness techniques. The variations of the micromechanical properties (indentation hardness) of the nanocomposites with nanotube content and with temperature are discussed in the light of the stress transfer between the polymer matrix and nanotubes, the degree of dispersion, the nature of the tubes and other structural parameters.     

Nonisothermal Crystallization Kinetics of Poly(lactic acid)/Nanosilica Composites

Poly(lactic acid) (PLA)/nanosilica composites were prepared by blending the PLA and nanosilica in chloroform and then evaporating the solvent to form the composite films in a dish. The Ozawa and Mo equations were used to characterize the nonisothermal cold crystallization kinetics of the PLA/nanosilica composites. The results indicated that the Ozawa equation was not successful while the Mo equation was successful to describe the nonisothermal crystallization kinetics of PLA/nanosilica composites. The values of crystallization activation energy (E _c) of the samples were calculated by the Kissinger method. Although the sample crystallization rates were enhanced with the increase of nanosilica content, the samples exhibited increased E _c in the presence of nanosilica. The results showed that nanosilica had an effect on both the nucleation and the crystal growth of PLA, promoting the nucleation but interfering with the molecular motion of PLA in the crystallization process.     

Deformation and Fracture Behavior of PP/Ash Composites

In the present work, the deformation and fracture behavior of PP/ash composites with different ash content was investigated. The effect of a silane coupling agent was also analyzed. From uniaxial tensile tests, an increase in the stiffness with ash content was found as a result of the incorporation of the stiffer filler within the PP matrix. On the other hand, a decrease in tensile strength and strain at break with filler loading was observed. This result was attributed to the increased number of debonded large particles with filler content, which subsequently led to the formation of critical-size flaws. On the other side, the composites displayed higher values of fracture parameters than the matrix as a result of the development of a particle induced toughening mechanism. However, fracture properties were also found to decrease with ash content. This could be attributed to the increase in the number of critical-size flaws that induced premature failure. The incorporation of a silane coupling agent in the formulations led to composites with slightly improved tensile and fracture properties. This was probably due to improved interaction between PP and ash in the first case and a better dispersion of ash particles in the matrix and/or changes in the crystallization behavior of PP, in the latter case.