Preparation and characterization of multiwalled carbon nanotube dispersions in polypropylene: Melt mixing versus solid‐state shear pulverization

Dispersions of multiwalled carbon nanotubes (MWNT) in polypropylene (PP) were prepared via conventional melt batch mixing and solid‐state shear pulverization. The properties and structure of each system were assessed via linear viscoelasticity, electrical conductivity, PP crystallization kinetics, dynamic mechanical analysis, scanning electron microscopy, and small angle X‐ray scattering. Increasing either the duration or the intensity of melt mixing leads to higher degrees of dispersion of MWNT in PP, although at the cost of substantial melt degradation of PP for long mixing times. Samples prepared by pulverization exhibit faster crystallization kinetics and higher mechanical stiffness than the melt blended samples, but in contrast show no measurable low frequency elastic plateau in melt rheology, and lower electrical conductivity than melt‐mixed samples. X‐ray scattering demonstrates that neither sample has uniform dispersion down to the single MWNT level. The results illustrate that subtle differences in the size and distribution of nanotube clusters lead to differences in the nanotube networks with strong impact on bulk properties. The results also highlight distinctions between conductive networks and load transfer networks and demonstrate that a complete and comparative picture of dispersion cannot be determined by simple indirect property measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1426–1436, 2009     

Synthesis and characterization of single‐wall‐carbon‐nanotube‐doped emeraldine salt and base polyaniline nanocomposites

Nanocomposites of polyaniline (PANI) and single‐wall carbon nanotubes (SWNTs) were prepared and characterized via resonance Raman and electronic absorption spectroscopy (ultraviolet–visible/near‐infrared). The chemical synthesis of PANI was performed in the presence of SWNTs in concentrations ranging from 10 to 50 wt % (SWNT/PANI). The obtained materials were hydrophilic, homogeneous composite compounds. The chemical interaction between PANI (in the conducting emeraldine salt form and in the insulating emeraldine base form) and metallic and semiconducting nanotubes was investigated. The emeraldine salt form of the polymer was significantly stabilized in the composite in comparison with plain PANI. A selective electronic interaction process between PANI and metallic SWNTs was found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 815–822, 2005     

Attapulgite and ultrasonic oscillation induced crystallization behavior of polypropylene

In this article, the effect of ultrasonic oscillation on the dispersed morphology of attapulgite in polypropylene (PP) and crystallizing kinetics of PP/attapulgite composites prepared through extrusion in the presence and the absence of ultrasonic oscillation were studied. X‐ray diffraction analysis results showed that ultrasonic oscillation did not change attapulgite crystal structure during extrusion in PP/attapulgite composites. On the other hand, scanning electron microscopy and transmission electron microscope photographs indicated that ultrasonic oscillation promoted the dispersion of attapulgite particles in PP matrix. The dispersed morphology of attapulgite and ultrasound oscillation affected the crystalline form, nucleation rate, crystallization temperature, crystallinity, and spherulite size of PP crystals. PP transcrystals were formed on the attapulgite particle surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2300–2308, 2007     

Crystallization,melting behavior,and morphology of PP/Novolac blends

The crystallization, melting behavior, and morphology of Polypropylene (PP) and PP/Novolac blends were studied by scanning electron microscopy, wide angle X‐ray diffraction, differential scanning calorimetry, and polarized optical microscope. The results showed that the crystallization of PP in PP/Novolac blends was strongly influenced by crystallization temperature, particles size of Novolac, crosslinking, and compatibilizer maleic anhydride‐grafted PP. The Novolac resin could not only affect the crystal structure, but also acted as effective nucleating agents, accelerating the crystallization of PP in the PP/Novolac blends. And the smaller the Novolac particles were, the more effective were the nucleating agent for PP crystallization. Avrami equation was used to analyze the isothermal crystallization kinetics of PP and PP/Novolac blends. The influences of curing and compatibilizer on the crystallization behavior of PP were rather complicated. The crystallization thermodynamics were estimated using the Hoffman theory. The incorporation of cured Novolac and compatibilizer evidently decreased the chain folding energy of PP. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3288–3303, 2006     

Crystallization behavior of polypropylene with or without sodium benzoate as a nucleating agent

The crystallization kinetics of polypropylene (PP) with or without sodium benzoate as a nucleating agent were investigated by means of DSC and polarized optical microscopy in isothermal and nonisothermal modes. A modified Avrami equation was applied to the kinetic analysis of isothermal crystallization. The addition of the nucleating agent up to its saturation concentration increased the crystallization temperature by 15 °C and shortened both the isothermal and nonisothermal crystallization half‐times. It was concluded that the sodium benzoate acted as a good nucleating agent for α‐form PP. By adding the nuclefier to PP, adequately controlled spherulites increased the mechanical properties including especially the Izod impact strength and shortened cycle time of PP. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1001–1016, 2001     

Structure–property relationships in polyamide 6/multi‐walled carbon nanotubes nanocomposites

Polyamide 6 (PA6)/multi‐walled carbon nanotubes (MWCNT) nanocomposites were produced by diluting a masterbach containing 20 wt % nanotubes using melt mixing. The influence of the addition of well dispersed MWCNT (as indicated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM)) on the thermal transitions, and crystallization behavior of the PA6 matrix is investigated. Differential scanning calorimetry (DSC) results show a reduction in heat capacity jump at the glass transition which is interpreted by an immobilized interfacial layer near the nanotubes. Furthermore, both DSC and X‐ray diffraction (XRD) measurements indicate that nanotubes favor the formation of the α crystalline form of PA6. These findings are correlated with the observed improvement of the storage modulus as revealed by dynamic mechanical thermal analysis (DMTA). Additionally, a new crystallization peak appears when MWCNT are added, and is attributed to the formation of a different morphology of the same type crystallite around the nanotubes walls (trans‐crystallinity). Finally, water sorption measurements show an increase of water content, normalized to the amorphous polymer fraction, in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 764–774, 2009     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

Nonisothermal crystallization kinetics of polypropylene/montmorillonite nanocomposites

The nonisothermal crystallization kinetics of poly(propylene) (PP) and poly(propylene)/organic‐montmorillonite (PP/Mont) nanocomposite were investigated by differential scanning calorimetry (DSC) with various cooling rates. The Avrami analysis modified by previous research was used to describe the nonisothermal crystallization process of PP and PP/Mont nanocomposite very well. The values of half‐time and Z_c showed that the crystallization rate increased with increasing cooling rates for both PP and PP/Mont nanocomposite, but the crystallization rate of PP/Mont nanocomposite was faster than that of PP at a given cooling rate. The activation energies were estimated by the Kissinger method, and the values were 189.4 and 155.7 kJ/mol for PP and PP/Mont nanocomposite, respectively. PP/Mont nanocomposite could be easily fabricated as original PP, although the addition of organomontmorillonite might accelerate the overall nonisothermal crystallization process. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 408–414, 2002; DOI 10.1002/polb.10101     

Morphology and nonisothermal crystallization of in situ microfibrillar poly(ethylene terephthalate)/polypropylene blend fabricated through slit‐extrusion,hot‐stretch quenching

This study describes the morphology and nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ micro‐fiber‐reinforced blends (MRB) obtained via slit‐extrusion, hot‐stretching quenching. For comparison purposes, neat PP and PET/PP common blends are also included. Morphological observation indicated that the well‐defined microfibers are in situ generated by the slit‐extrusion, hot‐stretching quenching process. Neat iPP and PET/iPP common blends showed the normal spherulite morphology, whereas the PET/iPP microfibrillar blend had typical transcrystallites at 1 wt % PET concentration. The nonisothermal crystallization kinetics of three samples were investigated with differential scanning calorimetry (DSC). Applying the theories proposed by Jeziorny, Ozawa, and Liu to analyze the crystallization kinetics of neat PP and PET/PP common and microfibrillar blends, agreement was found between our experimental results and Liu's prediction. The increases of crystallization temperature and crystallization rate during the nonisothermal crystallization process indicated that PET in situ microfibers have significant nucleation ability for the crystallization of a PP matrix phase. The crystallization peaks in the DSC curves of the three materials examined widened and shifted to lower temperature when the cooling rate was increased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 374–385, 2004     

Isothermal crystallization kinetics of polypropylene with silane functionalized multi‐walled carbon nanotubes

Multi‐walled carbon nanotubes (MWNTs) were functionalized with a silane coupling agent. The MWNTs were first coated with inorganic silica by a sol‐gel process and then grafted with 3‐methacryloxypropyltrimethoxysilane (3‐MPTS). The effect of raw MWNTs and silane‐functionalized MWNTs on the crystallization behavior of poly(propylene) (PP) was investigated by means of polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Results obtained from isothermal crystallization experiments indicate that 3‐MPTS functionalization affects the crystallization and melting behavior of PP/MWNTs composites remarkably, which can be attributed to the fact that 3‐MPTS functionalization of MWNTs leads to a uniform dispersion of MWNTs in PP matrix resulting in the good nucleating effect of MWNTs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1616–1624, 2007     

Effect of partial melting on the crystallization kinetics of nylon‐1212

The isothermal and nonisothermal crystallization kinetics of partially melted nylon‐1212 was investigated with differential scanning calorimetry. Because of partial melting, the pre‐existing crystals changed the crystallization mechanism and had a strong effect on the crystallization process. The Avrami exponent and interfacial free energy of the chain‐folded surface of partially melted nylon‐1212 were higher than those of completely melted nylon‐1212. The work of chain folding was determined to be 5.9 kcal/mol. The activation energy of the isothermal crystallization process was determined to be 399.1 kJ/mol, far higher than that of complete melting. The crystallization rate coefficient and Jeziorny analysis indicated that the ability of nonisothermal crystallization for partially melted nylon‐1212 was enhanced. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3222–3230, 2005     

Selective distribution,reinforcement, and toughening roles of MWCNTs in immiscible polypropylene/ethylene‐co‐vinyl acetate blends

Polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) nanocomposites with functionalized multiwalled carbon nanotubes (FMWCNTs) have been prepared. The dissolution experiment, transmission electronic microscope, and scanning electronic microscope characterizations prove that, in the nanocomposites with sea–island morphology, although some FMWCNTs are observed in both PP and EVA phases, most of FMWCNTs distribute at the interface; however, in the nanocomposites with cocontinuous morphology, FMWCNTs mainly distribute in EVA phase. Further results based on (differential scanning calorimetry) measurements show that the different dispersion states of FMWCNTs, which are resulted by the different melt blending sequences, result in the different crystallization behaviors of PP matrix. The mechanical measurements show that FMWCNTs exhibit apparent reinforcement and toughening effects for immiscible PP/EVA blends, and such effects are greatly dependent upon the blending sequences. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1882–1892, 2010     

Studies on the properties of polypropylene with a new silicon‐containing intumescent flame retardant

A new intumescent flame retardant (PSiNII), which contains silicon, phosphorus, and nitrogen elements, has been synthesized and incorporated into polypropylene (PP). Its effect on the properties of PP is investigated based on flame retardancy, thermal properties, mechanical properties, and morphologies. The flame retardancy is evaluated by the limiting oxygen index value. The thermal properties (oxidative behaviors and thermal stability) are investigated by thermogravimetric analysis under nitrogen and air atmosphere. The mechanical properties are researched based on the maximum tensile stress and relative strain at break. The morphologies of PP/PSiNII are studied by the scanning electron micrograph. Their flame retardancy and thermal stability are improved by introducing PSiNII. PP/PSiNII blends can achieve high fire performance and keep high mechanical property at the same time. During a fire, the melt‐dripping behaviors of PP‐containing PSiNII are improved. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2548–2556, 2005     

Crystallization of poly(butylene adipate) in the presence of nucleating agents

The effect of nucleating agents on the polymorphic crystallization behavior of poly(butylene adipate) (PBA) was studied with four kinds of commercially available nucleating agents, such as talc and boron nitride. The crystal structures of the α and β forms were studied with wide‐angle X‐ray diffraction. The β‐to‐α‐crystal transformation of PBA in the absence and presence of the nucleating agents in isothermal crystallization and nonisothermal crystallization processes was studied with differential scanning calorimetry and polarized optical microscopy. In both isothermal and nonisothermal crystallization, the introduction of nucleating agents selectively initiated the nucleation of the α‐form crystal, which was relatively slow in the absence of nucleating agents. The nucleating activity of the four kinds of nucleating agents in the crystallization of the PBA α‐form crystal was determined by the study of the nonisothermal crystallization, spherulite morphology, and isothermal kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2340–2351, 2005     

Crystallization behavior of dynamically cured polypropylene/epoxy blends

Dynamically cured polypropylene (PP)/epoxy blends compatibilized with maleic anhydride grafted PP were prepared by the curing of an epoxy resin during melt mixing with molten PP. The morphology and crystallization behavior of dynamically cured PP/epoxy blends were studied with scanning electron microscopy, differential scanning calorimetry, and polarized optical microscopy. Dynamically cured PP/epoxy blends, with the structure of epoxy particles finely dispersed in the PP matrix, were obtained, and the average diameter of the particles slightly increased with increasing epoxy resin content. In a study of the nonisothermal crystallization of PP and PP/epoxy blends, crystallization parameter analysis showed that epoxy particles could act as effective nucleating agents, accelerating the crystallization of the PP component in the PP/epoxy blends. The isothermal crystallization kinetics of PP and dynamically cured PP/epoxy blends were described by the Avrami equation. The results showed that the Avrami exponent of PP in the blends was higher than that of PP, and the crystallization rate was faster than that of PP. However, the crystallization rate decreased when the epoxy resin content was greater than 20 wt %. The crystallization thermodynamics of PP and dynamically cured PP/epoxy blends were studied according to the Hoffman theory. The chain folding energy for PP crystallization in dynamically cured PP/epoxy blends decreased with increasing epoxy resin content, and the minimum of the chain folding energy was observed at a 20 wt % epoxy resin content. The size of the PP spherulites in the blends was obviously smaller than that of PP. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1181–1191, 2004     

Morphological and mechanical properties of carbon nanotube/polymer composites via melt compounding

The mechanical properties and morphology of multiwall carbon nanotube (MWNT)/polypropylene (PP) nanocomposites were studied as a function of nanotube orientation and concentration. Through melt mixing followed by melt drawing, using a twin screw mini‐extruder with a specially designed winding apparatus, the dispersion and orientation of MWNTs was optimized in PP. Tensile tests showed a 32% increase in toughness for a 0.25 wt % MWNT in PP (over pure PP). Moreover, modulus increased by 138% with 0.25 wt % MWNTs. Transmission electron microscopy and scanning electron microscopy demonstrated qualitative nanotube dispersion and orientation. Wide angle X‐ray diffraction was used to study crystal morphology and orientation by calculating the Herman's orientation factor for the composites as function of nanotube loading and orientation. The addition of nanotubes to oriented samples causes the crystalline morphology to shift from α and mesophase to only α phase. Furthermore, the addition of nanotubes (without orientation) was found to cause isotropization of the PP crystal, and drawing was shown to improve crystal orientation through the orientation factor. In addition, differential scanning caloriometry qualitatively revealed little change in overall crystallinity. In conclusion, this work has shown that melt mixing coupled with melt drawing has yielded MWNT/PP composites with a unique combination of strength and toughness suitable for advanced fiber applications, such as smart fibers and high‐performance fabrics. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 864–878, 2006     

Preparation and characterization of PP/clay nanocomposites based on modified polypropylene and clay

X‐ray diffraction and differential scanning calorimeter (DSC) methods have been used to investigate the crystallization behavior and crystalline structure of hexamethylenediamine (HMDA)‐modified maleic‐anhydride‐grafted polypropylene/clay (PP‐g‐MA/clay) nanocomposites. These nanocomposites have been prepared by using HMDA to graft the PP‐g‐MA (designated as PP‐g‐HMA) and then mixing the PP‐g‐HMA polymer in hot xylene solution, with the organically modified montmorillonite. Both X‐ray diffraction data and transmission electron microscopy images of PP‐g‐HMA/clay nanocomposites indicate that most of the swellable silicate layers are exfoliated and randomly dispersed into PP‐g‐HMA matrix. DSC isothermal results revealed that introducing 5 wt % of clay into the PP‐g‐HMA structure causes strongly heterogeneous nucleation, which induced a change of the crystal growth process from a three‐dimensional crystal growth to a two‐dimensional spherulitic growth. Mechanical properties of PP‐g‐HMA/clay nanocomposites performed by dynamic mechanical analysis show significant improvements in the storage modulus when compared to neat PP‐g‐HMA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3242–3254, 2005     

Preparation of single‐walled carbon nanotubes‐induced poly(p‐oxybenzoyl) crystals

Crystallization of oligomers was applied for the preparation of single‐walled carbon nanotubes (SWNTs)/poly(p‐oxybenzoyl) (POB) crystals using SWNTs as a nucleating agent. Polymerization conditions were investigated to induce the crystallization of POB oligomers through SWNTs. SWNTs/POB plate‐like or lozenge‐shaped crystals were successfully prepared by direct polymerization of p‐hydroxybenzoic acid (HBA) in a mixed solvent of DMF/Py with TsCl in the presence of functionalized SWNTs. The size of the plate‐like crystals were ～200 nm to 3 μm. The crystals consisted of some layers, ～3 nm thick plates. Model reactions showed that esterification reactions proceed between functionalized SWNTs and HBA monomers in the polymerization system. The obtained crystals exhibited unique morphology and high crystallinity, producing a novel SWNT/POB hybrid. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1265–1277, 2008     

Poly(vinylidene fluoride)/clay nanocomposites prepared by melt intercalation: Crystallization and dynamic mechanical behavior studies

The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported for the first time. PVDF/clay nanocomposites were prepared by melt intercalation with organophilic clay. The composites were characterized with X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. X‐ray diffraction results indicated intercalation of the polymer into the interlayer spacing. PVDF in the nanocomposites crystallized in the β form. Differential scanning calorimetry nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity, as evidenced by the melting and crystallization peaks. Isothermal crystallization studies showed an enhanced rate of crystallization with the addition of clay, as evidenced by a reduction in the crystallization time. Dynamic mechanical analysis indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. The tan δ peak signifying the glass‐transition temperature of PVDF shifted to higher temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002     

Polypropylene/carbon nanotube magnetic composites obtained using carbon nanotubes from sawdust

Magnetic polypropylene (PP) nanocomposites with different loadings (from 0.5 to 20 wt %) of carbon nanotubes with iron (CNT‐Fe) were fabricated using the melt‐mixing method. The carbon nanotubes were synthesized by pyrolysis of sawdust from the furniture industry. The morphological characterization shows homogenous dispersion of the filler in the polymer matrix. The addition of only 0.5 wt % CNT‐Fe already results in ferromagnetic behavior in the diamagnetic polymer matrix. The thermal properties were investigated using thermogravimetric analysis and differential scanning calorimetry. The results show an increase in the maximum degradation, crystallization, and melting temperatures of the nanocomposites compared with neat PP. The nanocomposites showed improvement in terms of mechanical and oxygen permeability properties. A very significant result of the work is the high remnant magnetization and coercivity values of the nanocomposites at room temperature whereas most of the works on similar systems show magnetic properties only at very low temperatures.