Polyethylene/carbon nanotube nano hybrid shish-kebab obtained by solvent evaporation and thin-film crystallization

Crystallization of polymers on carbon nanotubes (CNTs) has resulted in a novel nano hybrid shish kebab (NHSK) structure, within which CNTs serve as the nucleation sites (shish) and polymer lamellar crystals form the kebabs. Previously reported NHSK structures were obtained by solution crystallization, bulk crystallization and physical vapor deposition methods. Herein we report a simple, rapid, yet effective approach to produce NHSK materials using solvent evaporation and thin film crystallization. Polyethylene (PE) was used as the model polymer. PE solution was drop cast on CNT-coated carbon films, and upon solvent evaporation, PE crystallized onto/near CNTs, following the template of the latter and NHSK structure was then formed. The final morphology was found to result from the competition between heterogeneous nucleation and homogeneous nucleation of PE. The formation of NHSK also strongly depends on the structure of CNTs as well as the molecular weight of PE. This work shows a facile method to form NHSK and to study CNT-induced crystallization under nonequilibrium conditions.     

Effect of molding temperature on crystalline and phase morphologies of HDPE composites containing PP nano-fibers

A high-density polyethylene (HDPE)/isotactic polypropylene (PP) (75/25) blend containing 25 wt% of PP was fibrillated by roller drawing at 138 °C. The fibrillated blend was processed again at temperatures ranging from 155 to 200 °C by compression molding or extrusion. The effects of molding temperature on the morphology and mechanical properties of the blend were investigated. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) were used to study the morphology of the samples. The roller-drawn blend exhibited a fibrous structure with the chain direction aligned parallel to the drawing direction. After molding at 155 °C, the HDPE formed parallel-stacked lamellae retaining the parallel orientation after the melting of the PE crystals. As the molding temperature increased the parallel orientation gradually vanished and some of the parallel-stacked lamellae changed into twisted lamellae. The PP phase existed as fibrils in the PE matrix and the crystals stayed with their molecular chain aligned parallel to the fibrillation direction even when the molding temperature was far above the melting temperature of PP. Nevertheless, the orientation of the crystals did not change as the molding temperature increased from 155 to 165 °C. The internal structure of the PP fibrils changed from a needle structure to a parallel-stacked one. The PP fibrils induced the crystallization of the PE melt, leading to the formation of a trans-crystalline layer at their surface. As the molding temperature increased, more PE lamellae protruded into the PP fibrils and the interface between the PP fibrils and the PE matrix became diffuse.     

Purification of multi-walled carbon nanotubes through microwave heating of nitric acid in a closed vessel

We demonstrate that microwave-assisted heating in 5 mL of nitric acid eliminates impurities, such as amorphous carbon, carbon nanoparticles, and metals, from multi-walled carbon nanotubes (MWNTs). Heating the closed reaction vessel under microwave irradiation at 160 °C for 30 min is a very effective means of purifying the MWNTs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images confirm that these reaction conditions are beneficial for removing the impurities and ensuring that the MWNTs remain intact. In contrast, a purification temperature of 180 °C provides too strongly oxidizing conditions that destroy the MWNTs. The ratio of the G and D bands in the Raman spectra also confirms that a temperature of 160 °C is optimal. The defect peak that we observed in the differential thermogravimetry (DTG) analysis of the raw material was not present after microwave purification. The presence of metal impurities in the MWNTs can be reduced significantly when using this method.     

Thermal and morphological characterization of composites prepared by solution crystallization method of high‐density polyethylene on carbon nanotubes

The morphology, nucleation, and crystallization of polyethylene/carbon nanotubes composites prepared by solution crystallization method of high density polyethylene on Multiwall Carbon Nanotubes (MWNTs) are studied. Transmission electron microscopy (TEM) results show that the center stems of MWNTs are decorated with lamellar crystals. The nonisothermal crystallization kinetics of pure PE and PE/MWNTs composites are investigated by differential scanning calorimetry at various cooling rates. It is found that the Avrami analysis modified by Jeziorny and Mo can describe the nonisothermal crystallization process of pure PE and PE/MWNTs very well. The difference in the value of exponent between PE and PE/MWNTs suggests that addition of the MWNTs influences the mechanism of nucleation and the growth of PE crystallites. On one hand, the increasing of temperature corresponding to the maximum rate of crystallization and the onset crystallization temperature and the study of the nucleation activity reveal that the inorganic component (MWNTs) can act as the nucleating agent to facilitate the crystallization of PE in the hybrids. On the other hand, the decreasing degree of crystallinity and the increasing of half‐crystallization time imply that the MWNTs networks confine the crystallization of PE. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis of titania/carbon nanotube heterojunction arrays for photoinactivation of E. coli in visible light irradiation

TiO₂/multi-wall carbon nanotube (MWNT) heterojunction arrays were synthesized and immobilized on Si(0 0 1) substrate as photocatalysts for inactivation of Escherichia coli bacteria. The vertically aligned MWNT arrays were grown on ∼5 nm Ni thin film deposited on the Si by using plasma enhanced chemical vapor deposition at 650 °C. Then, the MWNTs were coated by TiO₂ using dip-coating sol-gel method. Post annealing of the TiO₂/MWNTs at 400 °C resulted in crystallization of the TiO₂ coating and formation of Ti-C and Ti-O-C carbonaceous bonds at the heterojunction. The visible light-induced photoinactivation of the bacteria increased from MWNTs to TiO₂ to TiO₂/MWNTs, in which the bacteria could even slightly breed on the MWNTs. In addition, the TiO₂/MWNTs annealed at 400 °C showed a highly improved antibacterial activity than the TiO₂/MWNTs annealed at 100 °C. The excellent visible light-induced photocatalytic efficiency of the TiO₂/MWNTs/Si film annealed at 400 °C was attributed to formation of the carbonaceous bonds at the heterojunction, in contrast to the 100 °C annealed TiO₂/MWNTs/Si sample which had no such effective bonds.     

Coalescence of single-walled carbon nanotubes and formation of multi-walled carbon nanotubes under high-temperature treatments

Electric arc-discharge single-wall carbon nanotubes are annealed between 1600 and 2800 °C under argon flow. Their stability and evolution are studied by coupling TEM, X-ray diffraction and Raman spectroscopy. The first modifications appear at 1800 °C with a significant decrease of the crystalline order. It is due to SWNTs coalescence leading to smaller bundles but with an increase of the tube diameters from 2 to 4 nm. From 2200 °C, SWNTs progressively disappear to the benefit of MWNTs having at first two to three carbon layers then reaching 7 nm external diameter. The possible mechanisms responsible for the SWNTs coalescence and instability and their transformation in MWNTs are discussed.     

The effect of temperature on nascent morphology of polyethylene polymerized over solution-phase flat model catalysts

The structure and morphology of polyethylene (PE) produced during solution polymerization using bis(imino)pyridyl metal catalysts supported by flat SiO₂/Si(100) wafers were investigated by atomic force microscopy (AFM) and electron diffraction. Depending on the polymerization temperature, ranging from RT to 85 °C, different morphologies of the nascent PE have been observed. “Sea weed” like supermolecular structures are the predominant nascent morphologies of the PE polymerized at low temperatures. This should be associated with the high PE yield and high nucleation rate at low temperature; the catalyst is highly active and the PE macromolecules have low solubility in toluene and nucleate immediately after formation. With increasing polymerization temperature, e.g. at 60 or 70 °C, larger single crystals with roughly a lozenge shape but saw-tooth-like facets have been created. The multilayer overgrowth of the PE crystals demonstrates that the generated PE materials exceed what is required for single layer crystal growth. At 85 °C, decreasing crystal growth rate results in the formation of small PE single crystals. At the same time, the high solubility of the PE in toluene results in continuous diffusion of the macromolecules to the existing PE crystals and therefore single crystals in regular truncated lozenge shape have been formed. Electron diffraction indicates that in the whole temperature range, PE crystallizes in flat-on crystals in chain-folded structure with different chain folding stem length.     

Self-assembly and crystallization behavior of a double-crystalline polyethylene-block-poly(ethylene oxide) diblock copolymer

The self-assembly and crystallization behavior of a well-defined low molecular weight polyethylene-block-poly(ethylene oxide) (PE-b-PEO) diblock copolymer was studied. The number-average degrees of polymerization for the PE and PEO blocks were 29 and 20, respectively. The molecular weight distribution was 1.04 as determined by size-exclusion chromatography. The PE-b-PEO sample exhibited two melting points at 28.7 and 97.4 °C for the PEO and the PE crystals, respectively. The crystallization of the PE blocks was unconfined, while the crystallization of the PEO blocks was confined between pre-existing PE crystalline lamellae, as demonstrated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) studies. In the fully crystalline state, both PE and PEO blocks formed extended-chain crystals with PE chains tilted ∼22° from the lamellar normal and PEO chains parallel to the lamellar normal, as evidenced by two-dimensional WAXD study of shear-oriented samples. Regardless of hydrogen bonding among hydroxyl chain ends in the PEO blocks, interdigitated, single-crystalline layer morphology was observed for both PE and PEO crystals. The partial crystalline morphology, where the PE crystallizes and the PEO is amorphous, had the same overall d-spacing as the fully crystalline morphology. A double-amorphous PEO layer sandwiched between neighboring PE crystalline layers was deduced based on a chain conformation study using Fourier transform infrared. The confined crystallization kinetics for PEO blocks was investigated by differential scanning calorimetry, which could be explained by a heterogeneous nucleation mechanism. The slower crystallization rate in the PEO-block than the same molecular weight homopolymer was attributed to the effects of nanoconfinement and PEO chains tethered to the PE crystals.     

Effective reinforcement of carbon nanotubes in polypropylene matrices

This study describes an attempt to mechanically reinforce polypropylene (PP) using multi‐wall carbon nanotubes (MWNTs) through a melt compounding process followed by hot‐pressing and solid state drawing. The effect of a high density polyethylene (HDPE) coating on MWNTs and melt flow index (MFI) of PP on the dispersion of MWNTs and composite properties are studied by means of mechanical tests, transmission electron microscopy (TEM), scanning electron microscope (SEM), differential scanning calorimetry (DSC), and wide angle x‐ray diffraction (WAXD). Highly orientated composite tapes are prepared to fully utilize the properties of MWNTs in uniaxial direction. Highly aligned MWNTs are shown by SEM, while highly oriented polymer chains are characterized by WAXD. Composite theory is used to analysis the results and indicate that effective reinforcement of PP by MWNTs is highest at relatively low filler content and draw ratios. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Carbon nanotube induced polymer crystallization: The formation of nanohybrid shish-kebabs

Carbon nanotubes (CNTs) have attracted tremendous attention in recent years because of their superb optical, electronic and mechanical properties. In this article, we aim to discuss CNT-induced polymer crystallization with the focus on the newly discovered nanohybrid shish-kebab (NHSK) structure, wherein the CNT serves as the shish and polymer crystals are the kebabs. Polyethylene (PE) and Nylon 6,6 were successfully decorated on single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), and vapor grown carbon nanofibers (CNFs). The formation mechanism was attributed to “size-dependent soft epitaxy”. Polymer CNT nanocomposites (PCNs) containing PE, Nylon 6,6 were prepared using a solution blending technique. Both pristine CNTs and NHSKs were used as the precursors for the PCN preparation. The impact of CNTs on the polymer crystallization behavior will be discussed. Furthermore, four different polymers were decorated on CNTs using the physical vapor deposition method, forming a two-dimensional NHSK structure. These NHSKs represent a new type of nanoscale architecture. A variety of possible applications will be discussed.     

Structure and crystallization behavior of Nylon 66/multi-walled carbon nanotube nanocomposites at low carbon nanotube contents

Multi-walled carbon nanotubes (MWNTs) were modified with poly(hexamethylene adipamide) (also known as Nylon 66) via a controlled polymer solution crystallization method. A “nanohybrid shish kebab” (NHSK) structure was found wherein the MWNT resembled the shish while Nylon 66 lamellar crystals formed the kebabs. These Nylon 66-functionalized MWNTs were used as precursors to prepare polymer/MWNT nanocomposites. Excellent dispersion was revealed by optical and electron microscopies. Nitric acid etching of the nanocomposites showed that MWNT formed a robust network in Nylon 66. Non-isothermal DSC results showed multiple melting peaks, which can be attributed to lamellar thickness changes upon heating. The crystallite sizes L₁₀₀ and L₀₁₀ of Nylon 66, determined by WAXD, decreased with increasing MWNT contents. Isothermal DSC results showed that crystallization kinetics increased first and then decreased with increasing MWNT contents in Nylon 66. This study showed that the effect of MWNTs on Nylon 66 crystallization is twofold: MWNTs provide heterogeneous nucleation sites for Nylon 66 crystallization while the tube network structure hinders large crystal growth.     

Origin of various lamellar orientations in high-density polyethylene/isotactic polypropylene blends achieved via dynamic packing injection molding: bulk crystallization vs. epitaxy

Epitaxial growth of high-density polyethylene (HDPE) onto lamellae of isotactic polypropylene (iPP), with HDPE chains inclined about 50° to that of iPP, has been achieved for the first time in their blends via dynamic packing injection molding. Even more, the epitaxial growth was found to be dependent on composition of the blends. The sequence of crystallization is not the dominant factor, but the fact that iPP crystallizes before HDPE is prerequisite for epitaxial growth of PE. Various lamellar orientations with composition can be explained by the competition between bulk crystallization and epitaxy at interfaces (i.e. iPP lamellae). In 20PP (20 wt% iPP by weight in blends), HDPE can readily crystallize in the bulk as a result of shear, and no epitaxial growth of PE is observed. For 80PP, however, bulk crystallization of HDPE can be depressed due to lack of nuclei in its bulk, resulting from a much finer droplets dispersed in the iPP matrix, and then epitaxial growth prevails.     

Insight into growth details and characteristics of windmill-like polyethylene crystals

The crystallization detail of polyethylene (PE) has been scarcely studied via in-situ approach since it is an extremely fast process. In this work, optical microscopy is used to investigate crystallization details and characteristics of windmill-like polyethylene crystals. It has been shown that the straight edges of the petals appear firstly and grow in pairs from their central junctions, which subsequently induce the surrounding domains in between each pairs of petals to nucleate and crystallize into twisted lamellar overgrowths. The remaining terrace-stacked lamellae which form curved edges of the petals start to develop only after the straight edges of the petals together with the twisted lamellar overgrowths have completed their growth. It is confirmed that the preferential growth direction of these petals are along crystallographic [113] axis, which has an angle of 65° with the typical direction along b-axis adopted also by the twisted lamellar overgrowths. The crystallization kinetics is analyzed in terms of Avrami equation and an Avrami exponent n = 2 is thus obtained, which is consistent with the morphological observations of heterogeneous nucleation and 2-dimensional growth for these PE crystals. The melting behaviors of these crystals are exactly the reversed process of crystallization.     

Study on morphology and crystal growth of syndiotactic polystyrene solution-grown crystals by transmission electron and atomic force microscopy

The morphology of solution-grown crystals (SGCs) of syndiotactic polysthyrene (s-PS) has been investigated using transmission electron and atomic force microscopy (TEM and AFM). Well-defined s-PS SGCs were prepared from 0.005% (w/w) n-tetradecane/decahydronaphthalene solution 2:1 (v/v) by an isothermal crystallization method at 200 °C. Lattice constants for this crystal estimated by TEM with the diffraction mode are a=0.90 nm, b=2.88 nm. AFM images of the folded chains on the surface of s-PS SGC suggested their alignment parallel to the direction of the growth face of the truncated-lozenge shaped crystal. The angle between the growth faces obtained from s-PS SGCs was 130°. Since, the value of 130° correspond to the {230} angle, the primary growth face of s-PS SGC was assigned to the (230) plane.     

Controlling the diameter distribution of carbon nanotubes grown from camphor on a zeolite support

Single-wall and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively) of controlled diameter distribution were selectively grown by thermal decomposition of a botanical hydrocarbon, camphor, on a high-silica zeolite support impregnated with Fe-Co catalyst. Effects of catalyst concentration, growth temperature and camphor vapor pressure were investigated in wide ranges, and diameter distribution statistics of as-grown nanotubes was analyzed. High yields of metal-free MWNTs of fairly uniform diameter (∼10 nm) were grown at 600-700 °C, whereas significant amounts (∼30%) of SWNTs were formed at 850-900 °C within a narrow diameter range of 0.86-1.23 nm. Transmission electron microscopy and micro-Raman spectroscopy reveal that camphor-grown nanotubes are highly graphitized as compared to those grown from conventional CNT precursors used in chemical vapor deposition.     

Morphology of melt-quenched poly(ε-caprolactone)-block-polyethylene copolymers

The morphology of a melt-quenched crystalline-crystalline diblock copolymer, poly(ε-caprolactone)-block-polyethylene (PCL-b-PE), was studied by small-angle X-ray scattering and transmission electron microscopy. The melting behavior of PCL-b-PE was also investigated by differential scanning calorimetry. The melting temperature of PCL blocks, T_m,PCL, was ca. 55 °C and that of PE blocks was ca. 96 °C. Therefore, the PE block always crystallized first during quenching from the microphase-separated melt into various temperatures T_c below T_m,PCL to yield an alternating structure composed of PE lamellae and amorphous layers (PE lamellar morphology), and subsequently the crystallization of PCL blocks started at T_c after some induction period. The PE lamellar morphology was preserved after the crystallization of PCL blocks at low crystallization temperatures (T_c<30 °C), that is, the PCL block crystallized within the PE lamellar morphology. At high crystallization temperatures (45 °C>T_c>30 °C), on the other hand, the crystallization of PCL blocks destroyed the PE lamellar morphology to result in a new lamellar morphology mainly consisting of PCL lamellae and amorphous layers (PCL lamellar morphology). The PE crystals were fragmentarily dispersed in the PCL lamellar morphology.     

Composition dependence of crystallized lamellar morphology formed in crystalline-crystalline diblock copolymers

We have investigated the crystallized morphology formed at each temperature T_c (20 °C ≤ T_c ≤ 45 °C) in double crystalline poly(?-caprolactone)-block-polyethylene (PCL-b-PE) copolymers as a function of composition (or volume fraction of PE blocks ?_PE) by employing small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) techniques. When PCL-b-PE with ?_PE ≤ 0.58 was quenched from a microphase-separated melt into T_c, the crystallization of PE blocks occurred first to yield an alternating structure consisting of thin PE crystals and amorphous PE + PCL layers (PE lamellar morphology) followed by the crystallization of PCL blocks, where we can expect a competition between the stability of the PE lamellar morphology (depending on ?_PE) and PCL crystallization (on T_c). Two different morphologies were formed in the system judging from a long period. That is, the PCL block crystallized within the existing PE lamellar morphology at lower T_c (<30 °C) to yield a double crystallized alternating structure while it crystallized by deforming or partially destroying the PE lamellar morphology at higher T_c (>35 °C) to result in a significant increase of the long period. However, the temperature at which the morphology changed was almost independent of ?_PE. For PCL-b-PE with ?_PE ≥ 0.73, on the other hand, the morphology after the crystallization of PE blocks was preserved at every T_c investigated.     

Unusual crystallization of polyethylene at melt/atomically flat interface: Lamellar thickening growth under normal pressure

The morphology of polyethylene (PE) crystallized at the melt/atomically flat substrate interface was studied using atomic force microscopy (AFM). Our attention is concentrated on isothermal crystallization of PE on HOPG and MoS₂ substrates at high temperatures up to 135 °C. By quenching after different times of crystallization, it was possible to “freeze” the lamellar morphology at various stages of its development at a given supercooling. After detachment of the PE sample from the substrate, individual lamellae (even 150 nm thick) and stacks of the edge-on lamellae after different stages of growth were observed. The similarity of the individual lamellae with those grown from the hexagonal phase under high pressure (characteristic tapered edges), allows to conclude that at the interface, even under normal pressure, the crystallization proceeds according to the mechanism of lamellar thickening growth.     

Crystal orientation of poly(?-caprolactone) blocks confined in crystallized polyethylene lamellar morphology of poly(?-caprolactone)-block-polyethylene copolymers

The crystal orientation of poly(?-caprolactone) (PCL) blocks in PCL-block-polyethylene (PE) copolymers has been investigated using two-dimensional small-angle X-ray scattering (2D-SAXS) and 2D wide-angle X-ray diffraction (2D-WAXD) as a function of crystallization temperature T_c and thickness of PCL layers d_PCL. The PCL blocks were spatially confined in the solid lamellar morphology formed by the crystallization of PE blocks (PE lamellar morphology), an alternating structure of crystallized PE lamellae and amorphous PCL layers. This confinement is expected to be intermediate between hard confinement by glassy lamellar microdomains and soft confinement by rubbery ones, because the crystallized PE lamellae consist of hard PE crystals covered with amorphous (or soft) PE blocks. The 2D-SAXS results showed uniaxial orientation of the PE lamellar morphology after applying the rotational shear to the sample. Therefore, it was possible to investigate crystal orientation of PCL blocks within the oriented PE lamellar morphology. The 2D-WAXD results revealed that the c axis of PCL crystals (i.e., stem direction of PCL chains) was parallel to the lamellar surface normal irrespective of T_c when 16.5 nm ≥ d_PCL ≥ 10.7 nm. However, it changed significantly with changing T_c when d_PCL = 8.8 nm; the c axis was perpendicular to the lamellar surface normal at 45 °C ≥ T_c ≥ 25 °C while it was almost random at 20 °C ≥ T_c ≥ 0 °C. These results suggest that the PE lamellar morphology plays a similar role to glassy lamellar microdomains regarding spatial confinement against subsequent PCL crystallization.     

Pyrolysis of a fraction of waste polypropylene and polyethylene for the recovery of BTX aromatics using a fluidized bed reactor

Fractions of waste polypropylene and polyethylene were pyrolyzed in a pyrolysis plant under different conditions. In this study, the influence of the reaction temperature (650-750 °C), the feed rate, and the kind of fluidizing medium on the product spectrum were investigated. Pyrolysis of the PP fraction produced oils up to 43 wt. % of the product. With respect to the PE fraction, the maximum oil yield was above 60 wt. % of the product. The target compound was BTX aromatics, whose amount in the oils reached 53 wt.% for the PP fraction and 32 wt. % for the PE fraction. It was shown that the PE fraction yielded a higher liquid product compared to the PP fraction, and that the concentration of aromatics in the oil increased at higher reaction temperatures for both the PP and PE fractions. A higher feed rate and the use of a gas product as the fluidizing medium were favored for the production of oils for both the PP and PE fractions. The oils that were obtained in the experiments almost had no metal and chlorine contents. The maximum heating value of the gas obtained in the experiments was about 50 MJ/kg.