Nanohybrid shish kebab structure and its effect on mechanical properties in poly(L‐lactide)/carbon nanotube nanocomposite fibers

In our previous work, the formation of a nanohybrid shish kebab (NHSK) structure was successfully achieved in helical polymer systems promoted by using single‐walled carbon nanotube (CNT) bundles with a unique ‘groove structure’, which is of great crystallographic interest. To further investigate the effect of surface groove structure of CNT bundles on the formation of NHSK structure in helical polymer systems, in the work reported here double‐walled carbon nanotube (DWNT) fibers with bundle structure were used as nucleating agents and orientation templates for poly(L ‐lactide) (PLLA) crystallization. A fine NHSK structure with controlled lateral size and period of kebabs was successfully obtained under various experimental conditions by using DWNT bundles. This could be due to the geometric confinement effect of the surface groove structure of the DWNT bundles, which could facilitate the orientation of PLLA chains along the DWNT axis and the lateral formation of a stable nucleus. Our work suggests an efficient method for the functionalization of CNTs with biocompatible PLLA, which may have some potential applications in biomedical areas. In addition, it is demonstrated that the formation of NHSK structure can effectively improve the physical bonding between PLLA and nanotubes, thus significantly improving the mechanical properties of PLLA/CNT nanocomposite fibers. Copyright © 2012 Society of Chemical Industry     

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.     

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.     

Hierarchical structure of injection-molded bars of HDPE/MWCNTs composites with novel nanohybrid shish-kebab

Injection-molded products usually show hierarchical structure from skin to core due to the existence of shear gradient and temperature gradient. Investigating the hierarchical structure is helpful to better understand the structure-property relationship of injection-molded sample, which is important for design and preparation of polymer products with high performance. In this work, the hierarchical structures of injection-molded bars of high-density polyethylene (HDPE)/multi-walled carbon nanotubes (MWCNTs) composite were explored by examining the microstructure and crystal morphology, layer by layer, along the sample thickness, using SEM, DSC and 2D-WAXS. To enhance the shear effect, a so-called dynamic packing injection molding (DPIM) technique was used to prepare the molded bar with high orientation level. Interestingly, SEM revealed that in the skin and core zones, the lamellae of PE anchored randomly on the surface of MWCNTs, while well-defined nanohybrid shish-kebab (NHSK) entities, in which fibrillous carbon nanotubes (CNTs) act as shish while HDPE lamellae act as kebab, exist in the oriented zone. The changed NHSK crystal structure along the thickness direction of molded bar is considered as due to the shear gradient and thermal gradient in injection molding. And the underlying origin of in situ formation of NHSK under shear effects is discussed based on experimental observations.     

聚乙烯-碳纳米管串晶的高效制备(英文)

We report a novel method to prepare nanohybrid shish-kebab (NHSK) structure of polyethylene (PE) and carbon nanotube (CNT). Pristine CNTs without surface modification with high concentration was effectively dispersed in xylene solution by a simple shearing method, which induces the quick crystallization of PE in xylene to form a novel NHSK structure with more dense and smaller PE kebab on CNT axis. The flocculated NHSK product was transferred quickly from the xylene solution to the ethanol solution, in order to shorten the preparation time. The freeze-drying method was used in vacuum instead of high-temperature drying to avoid the aggregation of NHSK product. These improvements allow the formation of NHSK with an absolute yield of 200 mg·h-1 , which is 2000 folds of that reported previously. It is favorable to apply this structured material in high performance nanocomposite, by improving the compatibility of CNTs in polymer and the interfacial force between CNTs and polymer.     

Single wall carbon nanotube dispersion and exfoliation in polymers

Dispersion and exfoliation of single wall carbon nanotubes (SWNTs) have been studied in poly(acrylonitrile) (PAN), poly(p‐phenylene benzobisoxazole) (PBO) solutions, and composite fibers using transmission electron microscopy. As a result of polymer assisted dispersion and exfoliation, the average SWNT bundle diameter in SWNT/PAN (5/95) was 11 nm, while the average diameter for the pristine SWNT bundles was about 30 nm. High resolution TEM of SWNT/PBO (10/90) composite fibers did not reveal the presence of SWNT aggregates or bundles, suggesting SWNT exfoliation as individuals. On the other hand, both oriented and unoriented nanotube bundles have been observed in SWNT/PBO samples containing 15 wt % nanotubes. Carbon nanotubes are 10⁵ times more radiation resistant than flexible polymers such as polyethylene, and 10³ times more resistant than highly radiation resistant polymers such as PBO. Therefore in the high resolution TEM study of nanotube/polymer composites, nanotubes can be observed long after the polymer has been damaged by electron radiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 985–989, 2005     

Effect of temperature on the selection of semiconducting single walled carbon nanotubes using Poly(3-dodecylthiophene-2,5-diyl)

We report on the investigation of the temperature effect on the selective dispersion of single-walled carbon nanotubes (SWNTs) by Poly(3-dodecylthiophene-2,5-diyl) wrapping. The interaction mechanism between polymer chains and SWNTs is studied by controlling the polymer aggregation via variation of the processing temperature. Optical absorption and photoluminescence measurements including time resolved photoluminescence spectroscopy are employed to study the degree of interaction between the polymer in different aggregation states and the carbon nanotubes. At low processing temperatures, results are consistent with the planarization of the polymer chains and with SWNTs working as seeds for polymer aggregation. The formation of small clusters due to the inter-digitation of alkyl tails between neighboring polymer-wrapped SWNTs allows the formation of the SWNT bundles, as experimentally evidenced and investigated by molecular dynamics simulations. The interaction between the tubes within the bundles, which is reflected in the variation of the photoluminescence dynamics of the polymer, can be suppressed by warming up the sample.     

Carbon nanotube core–polymer shell nanofibers

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) and SWNT/polyacrylonitrile composite nanofibers were electrospun with SWNT bundles as the cores and the polymers as the shells. This was a novel approach for processing core (carbon nanotube)–shell (polymer) nanofibers. Raman spectroscopy results show strain‐induced intensity variations in the SWNT radial breathing mode and an upshift in the tangential (G) and overtone of the disorder (G′) bands, suggesting compressive forces on the SWNTs in the electrospun composite fibers. Such fibers may find applications as conducting nanowires and as atomic force microscopy tips. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1992–1995, 2005     

Investigation of molecular interaction between single‐walled carbon nanotubes and conjugated polymers

Single‐walled carbon nanotubes (SWNTs) have unique properties such as high electrical conductivity and high tensile strength. Their composites with polymers have a great role in new sciences such as organic solar cells and ultrastrong lightweight materials. In this article, molecular dynamic simulations with polymer consistent force field are performed to study the interaction between SWNTs and conjugated polymers including poly(2‐methoxy‐5‐(3‐7‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO‐PPV), poly(3‐hexythiophene) (P3HT), and poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐bis(N,N′‐(4,butylphenyl))bis(N,N′‐phenyl‐1,4‐phenylene)diamine] (PFB). We computed the interaction energy and morphology of polymers adsorbed to the surface of SWNTs was studied by the radius of gyration (Rg). The influence of important factors such as SWNT radius, chirality, and the temperature on the interfacial adhesion of SWNT–polymer and Rg of polymers were studied. We found that the strongest interaction between the SWNTs and these polymers was, first observed for P3HT, then MDMO‐PPV, and finally PFB. Our results showed that the interaction energy is influenced by SWNT radius and the specific monomer structure of the polymers, but the effects of chirality and temperature are very weak. In addition, we found that the temperature, chirality, and radius have not any important effect on the radius of gyration. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

聚合物串晶结构制备研究进展

综述了聚合物串晶结构的制备方法,其中主要有熔融挤出流延法、熔融纺丝法和溶液结晶法等。讨论了聚合物串晶结构形成和生长机理的研究进展。研究表明,各向同性熔体的分子链会发生折叠而形成球晶,而取向熔体的分子链会被拉伸伸直而形成串晶。串晶结构（shish-kebab）形成过程中,由伸直链晶体组成的部分（shish）和由折叠链晶体组成的部分（kebab）是同时形成的。最后对串晶结构的应用前景提出了展望。     

Phenomenological characterization of fabrication of aligned pristine‐SWNT and COOH‐SWNT nanocomposites via dielectrophoresis under AC electric field

Dielectrophoresis under the application of AC electric fields is one of the primary fabrication techniques (DEPFT) for obtaining aligned carbon nanotube (CNT)–polymer nanocomposites, and is used here to generate data sets from which DEPFT fabrication models in terms of CNT dispersion and orientation distribution can be developed. While the general understanding of how CNTs form aligned filaments under the influence of dielectrophoretic forces and moments is well established, detailed multi‐CNT‐filament formation predictions of microstructure evolution from a random dispersion into a more ordered structure remain intractable. As such, effort here is focused towards the development of phenomenological fabrication models for controlling local CNT dispersion and orientation as a function of applied electric field magnitude, frequency, and exposure time. In this study, 0.03 wt% single‐wall nanotubes (SWNTs) and acid treated functionalized SWNTs (COOH‐SWNTs) were dispersed in a photopolymerizable monomer blend (urethane dimethacrylate (UDMA) and 1,6‐hexanediol dimethacrylate (HDDMA)). Ultrasonication techniques were used to obtain the two different acrylate solutions i.e., 0.03% SWNTs/ UDMA/ HDDMA(9/1) solution and a 0.03% COOH‐SWNTs/UDMA/HDDMA(9/1) solution, consisting of randomly oriented, well dispersed SWNTs. Pristine SWNTs and acid treated SWNTs solutions were then subjected to controlled AC electric fields in order to explore the formation of aligned SWNT‐filaments. To assess key morphological features of the as‐produced SWNT‐acrylate and SWNT‐COOH‐acrylate nanocomposite samples, such as SWNT distribution and filament thicknesses, transmission optical microscopy has been used to observe the SWNT alignment and filament formation obtained by digitally mapping individual overlapping images. The acquisition of a large field of view with high magnification allows statistically meaningful distribution functions for morphological features to be constructed. Measurements of the as‐produced nanocomposite electrical properties in the SWNT alignment direction and transverse to it were used as a macroscale measure to confirm alignment and contiguity of the SWNT‐filament structure, with polarized Raman spectroscopy used to assess the degree of SWNT alignment at the local microscale level. It is observed that a combination of exposure time to AC electric field, and its frequency, is the key driver of filament thickness and spacing and that in general, the COOH‐SWNTs align to a greater extent than the pristine SWNTs, though they do not form filaments that are as thick and contiguous for the exposure times studied. POLYM. COMPOS., 36:1266–1279, 2015. © 2014 Society of Plastics Engineers     

Rapid, low temperature microwave synthesis of novel carbon nanotube-silicon carbide composite

Single wall carbon nanotubes (SWNTs) incorporated into ceramic matrices are known to impart enhanced mechanical, thermal and electrical properties to the composites formed. Current procedures for their synthesis face challenges, such as, the non-uniform dispersion of the SWNTs and their damage during high temperature processing in a reactive environment. These have led to poor interfacial matrix to SWNT adhesion and the ineffective utilization of the unique properties of the nanotubes. Here we report a rapid, low temperature microwave-induced reaction to create a novel nanoscale silicon carbide (SiC)-SWNT composite. The reaction, which was completed in 10 min, involves the decomposition of chloro-trimethylsilane and the simultaneous nucleation of nanoscale SiC spheres on the SWNT bundles. The bulk composite is a branched tree-like structure comprised of three-dimensionally arrayed SiC-SWNTs. The uniqueness of this approach lies in the formation of a ceramic directly on the SWNTs, rather than physical mixing, or the growth of nanotubes in a ceramic matrix.     

Influence of high molecular weight component on the hierarchical crystalline structures of injection‐molded bars of polyethylene

A small amount of high molecular weight molecules can have a dramatic influence on the flow‐induced crystallization kinetics and orientation of polymers. To elucidate the effects of the high molecular weight component under a real processing process, we prepared model blends in which high density polyethylene with a high molecular weight and wide molecular weight distribution was blended with a metallocene polyethylene with a low molecular weight and very narrow molecular weight distribution. To enhance the shear strength, gas‐assisted injection molding was utilized in producing the molded bars. The hierarchical structures and orientation behavior of the molded bars were intensively explored by using scanning electron microscopy and two‐dimensional wide‐angle X‐ray diffraction, focusing on effects of the high molecular weight component on the formation of the shish kebab structure. It was found that there exists a critical concentration of high molecular weight component for the formation of a shish kebab structure. The threshold was about 5.5–7.0 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. Moreover, the rheological properties of molten polyethylene melts were studied by dynamic rheological measurements and a critical characteristic relaxation time for shish kebab formation was obtained under the processing conditions adopted in this research. © 2013 Society of Chemical Industry     

Synergistic enhancement of crystallization and mechanical performance of polypropylene random copolymer by strong shear and β‐nucleating agent

Investigation of microstructure and properties is critical for the development and application of polymer materials. Polypropylene random copolymer (PPR) and β‐nucleated PPR are widely used in water pipe production. The effect of melt shear flow on the crystalline structure and mechanical properties of PPR containing β‐nucleating agent needs in‐depth understanding. In this paper, we demonstrated the preparation of PPR and PPR containing 0.1 wt% calcium pimelate (Ca‐Pim) samples by conventional injection molding (CIM) and oscillation shear injection molding (OSIM). The multilayer structures and morphologies of the samples were characterized by SEM, two‐dimensional X‐ray scattering and DSC. The mechanical properties and the microstructures of samples prepared by these two injection molding methods were compared. Compared with samples prepared by CIM, the stronger shear provided by OSIM induced the formation of a thicker layer of a shish‐kebab structure and a higher content of γ crystals, and dramatically suppressed the β‐nucleating effect of Ca‐Pim. The OSIM samples have more shish‐kebab structures and higher crystallinities than CIM samples and therefore the former exhibit better rigidity than the latter. The β crystals in the core layer and the thicker layer of shish‐kebab structure endow OSIM‐PPR/0.1 wt% Ca‐Pim with excellent impact toughness. © 2017 Society of Chemical Industry     

Covalent functionalization of single walled carbon nanotubes with peptide nucleic acid: Nanocomponents for molecular level electronics

Imparting molecular recognition to carbon nanotubes (CNTs) by conjugating them with bio-molecules has been an area of great interest as the resulting highly functionalized CNT-bioconjugates find their applications in various fields like molecular level electronics, pharmaceuticals, drug delivery, novel materials and many others. In this work we demonstrate the synthesis of functionally engineered single walled carbon nanotubes (SWNTs)-peptide nucleic acid (PNA) conjugates especially for nanoelectronic applications. Here we exploited the exceptional structural and chemical advantages of PNA (an artificial analogue of DNA) to join SWNTs ropes. SWNT-PNA-SWNT conjugates were synthesized using carbodiimide coupling chemistry and characterized by host of techniques like scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy. The results from different techniques confirm the formation of these conjugates. Theoretical analysis of molecular orbitals obtained by quantum mechanical simulations show that the highest occupied molecular orbital is located on the glutamate linker and that this interface state will align closely to the valence band of the extended SWNT facilitating charge transfer. The unique electrical and structural properties of these conjugates make them a potential candidate for application in CNT based nanodevices.     

Interaction between two single-walled carbon nanotubes revisited: Structural stability of nanotube bundles

On the basis of the all-atom model, cohesive energies per carbon atom between two single-walled carbon nanotubes (SWNTs) of uniform and different diameters were calculated, and structural stability of SWNT bundles with differing diameters was analyzed. It is found that the cohesive energy per carbon atom exhibits a minimum when the diameter of one tube is a half of that of the other. So we predict that the SWNT bundle formed by two species of tubes with the diameters of D and D/2 is a novel stable structure. In particular, an energy of 17.44 meV per carbon atom is needed for the separation of a single tube of 2.713 nm from the stable arrangement, while only 15.88 meV per carbon atom for the separation of a single tube of 2.713 nm from the hexagonal array of SWNTs of uniform size, which suggests that the special arrangement structure is more stable than the hexagonal array. It is expected that the calculated cohesive energies per carbon atom may provide valuable information for separation and physical properties of the SWNT bundles with differing diameters.     

Fiber Formation in Medium and Ultra‐High‐Molecular‐Weight Polyhydroxybutyrate Blends under Shear Flow

Summary: Polyhydroxybutyrate (PHB) is an ideal bioplastic, however, this polymer undergoes a severe embrittlement process because of its spherulitic structure, rendering the material brittle. Using a series of in‐situ rheo techniques, we have previously observed only the rapid initial stage of shish formation, we term a partial shish, which existed at high shears in medium‐molecular‐weight PHB, = 360 000. The shish kebab morphology is anticipated to remove or severely lessen this embrittlement process whilst providing new properties and applications. For medium and ultra high‐molecular‐weight (MMWT, = 360 000/UHMWT, = 5 × 10⁶) PHB 99/1 and 99.5/0.5 blends only a partial shish is identified. However, the initial shish formation stage and subsequent stages were observed at 98/2 and 97/3 blend ratios resulting in a complete shish, we term the full shish, and fiber formation was evident. We believe this fiber morphology achieved by high molecular weights is crucial to sustaining the shish kebab structure for an excessive period.

Left: In‐situ rheo‐light scattering micrograph; 97/3 MMWT/UHMWT PHB at 100 s^?1 for 1 s shear shish held at 75 s. Right: In situ rheo‐optical micrograph; PHB fiber morphology observed at 50 s^?1 for 2 s shear 98/2 MMWT/UHMWT PHB after 1 min.     

Structural development of gel-spinning UHMWPE fibers through industrial hot-drawing process analyzed by small/wide-angle X-ray scattering

The ultrahigh molecular weight polyethylene (UHMWPE) fibers were obtained directly from the industrial production line. Two-step industrial hot-drawing-to-specific-drawing ratios were carried out at the temperature of 120 and 130 °C, respectively. Small-angle X-ray scattering (SAXS) measurements using synchrotron radiation were applied to study the evolution of kebab structure and the formation of shish structure. The slight increase of long period and the rapid decrease of lateral sizes indicated the destruction of original lamellae which was accomplished by chain slip resulted in the orientation of lamellae to form shish structure. The decrease of average shish length was explained that the formed new shish structure had shorter shish length than the original shish at the early stage with the high concentration of spinning solution. Wide-angle X-ray diffraction (WAXD) measurements were performed to explore the changes of the degree of orientation of the crystals. It was found that the elevated drawing temperature was benefited to the evolution of the orientational order. The DSC result confirmed the evolution of shish–kebab structure through the melting behavior.     

Shish Kebab Morphology induced in Polyhydroxybutyrate under Shear Flow

Summary: In‐situ rheo small‐angle X‐ray scattering (SAXS), rheo‐light scattering, and rheo‐optical methods were employed to investigate the resultant morphology of polyhydroxybutyrate (PHB) under varying shear flow conditions. Immediately after shear flow application, a highly orientated structure emerged and row nucleation was identified at high shears. Only the initial stages of shish growth (we term the partial shish) were confirmed at excessively high shear conditions. However, only the kebabs were identified at medium shears, below this neither the shish nor kebab were observed. We believe this partial shish is a result of insufficient stability resulting from using such a low‐molecular‐weight species. We conclude that from our observations the shish kebab mechanism appears to display similarities to the Janeschitz‐Kriegl model of precursor formation.

Left: In‐situ rheo‐SAXS two‐dimensional pattern; kebab morphology observed at 100 s^?1 for 1 s shear after 160 s. Right: In‐situ rheo‐optical micrograph; PHB row‐nucleated morphology observed at 100 s^?1 for 1 s shear after 1 min.