Marilyn L. Minus

Structural Polymer-Based Carbon Nanotube Composite Fibers: Understanding the Processing–Structure–Performance Relationship

Among the many potential applications of carbon nanotubes (CNT), its usage to strengthen polymers has been paid considerable attention due to the exceptional stiffness, excellent strength, and the low density of CNT. This has provided numerous opportunities for the invention of new material systems for applications requiring high strength and high modulus. Precise control over processing factors, including preserving intact CNT structure, uniform dispersion of CNT within the polymer matrix, effective filler–matrix interfacial interactions, and alignment/orientation of polymer chains/CNT, contribute to the composite fibers’ superior properties. For this reason, fabrication methods play an important role in determining the composite fibers’ microstructure and ultimate mechanical behavior. The current state-of-the-art polymer/CNT high-performance composite fibers, especially in regards to processing–structure–performance, are reviewed in this contribution. Future needs for material by design approaches for processing these nano-composite systems are also discussed.

Polyethylene Crystallization Nucleated by Carbon Nanotubes under Shear

Polyethylene crystallization under shear has been studied in the presence of single-wall, few-wall, and multiwall carbon nanotubes (SWNT, FWNT, and MWNT). Polyethylene crystal d-spacings for (110) and (200) planes in polyethylene/carbon nanotubes (CNT) are smaller than in the control polyethylene without CNT and the polymer chain is oriented along the CNT axis. The single-wall carbon nanotube templated polyethylene crystals do not redissolve in boiling xylenes; instead, the chain morphology transforms to an amorphous conformation but remains oriented along the nanotube axis. SWNT crystal peaks were also observed in polyethylene/SWNT fibers.

Tailoring polyacrylonitrile interfacial morphological structure by crystallization in the presence of single-wall carbon nanotubes.

In order to improve stress transfer between polymer matrixes and nanofillers, controlling the structure development in the interphase region during composite processing is a necessity. For polyacrylonitrile (PAN)/single-wall carbon nanotubes (SWNT) composites, the formation of the PAN interphase in the presence of the SWNT as a function of processing conditions is studied. Under these conditions, three distinct interfacial coating morphologies of PAN are observed on SWNT. In the semidilute polymer concentration regime subjected to shearing, PAN extended-chain tubular coatings are formed on SWNT. Dilute PAN/SWNT quiescent solutions subjected to cooling yields hybrid periodic shish-kebab structures (first observation for PAN polymer), and dilute PAN/SWNT quiescent solutions subjected to rapid cooling results in the formation of an irregular PAN crystalline coating on the SWNT.

Polyacrylonitrile/Carbon Nanotube Composite Films

Reinforcement efficiency of different types of carbon nanotubes (CNT) have been compared in polyacrylonitrile (PAN) films at nanotube loadings of 5, 10, and 20 wt %. The films are characterized for mechanical, dynamic-mechanical, and thermomechanical properties, electrical conductivity, as well as structural analysis. PAN/CNT composite films exhibit electrical conductivities up to 5500 S/m. Based on X-ray diffraction, PAN crystallinity was shown to increase with the presence of CNT. PAN-CNT interactions in the various composites were compared using conventional activation energy analysis. The strongest physical interaction between PAN and CNT was found in samples containing single-wall carbon nanotubes (SWNT). CNT surface area was also measured using nitrogen gas adsorption and correlated with PAN-CNT composite film mechanical properties, in an effort to better understand PAN-CNT interactions for different CNT morphologies. Solvent behavior of various composite films has also been investigated. The presence of CNT was found to improve PAN solvent resistance.

Observations on Solution Crystallization of Poly(vinyl alcohol) in the Presence of Single-Wall Carbon Nanotubes.

PVA/SWNT dispersions yield aloe plant-like crystals, where the leaves are single crystals templated by PVA coated SWNT. Longer growth times (≈18 months) lead to hexagonal rod-like crystals. HR-TEM images show evidence that PVA molecules are aligned parallel to the SWNT axis. WAXD, electron diffraction, and HR-TEM observations of these aloe plant and hexagonal crystals suggests evidence for possible PVA-SWNT epitaxy. Wide-angle and electron diffraction data of these crystals also show that the structure seems to mimic the 2D hexagonal crystal packing of SWNT. PVA lattice images and moiré fringes were also observed in the leaf-like crystals.

Processing bulk natural wood into a high-performance structural material

Synthetic structural materials with exceptional mechanical performance suffer from either large weight and adverse environmental impact (for example, steels and alloys) or complex manufacturing processes and thus high cost (for example, polymer-based and biomimetic composites). Natural wood is a low-cost and abundant material and has been used for millennia as a structural material for building and furniture construction. However, the mechanical performance of natural wood (its strength and toughness) is unsatisfactory for many advanced engineering structures and applications. Pre-treatment with steam, heat, ammonia or cold rolling followed by densification has led to the enhanced mechanical performance of natural wood. However, the existing methods result in incomplete densification and lack dimensional stability, particularly in response to humid environments, and wood treated in these ways can expand and weaken. Here we report a simple and effective strategy to transform bulk natural wood directly into a high-performance structural material with a more than tenfold increase in strength, toughness and ballistic resistance and with greater dimensional stability. Our two-step process involves the partial removal of lignin and hemicellulose from the natural wood via a boiling process in an aqueous mixture of NaOH and Na2SO3 followed by hot-pressing, leading to the total collapse of cell walls and the complete densification of the natural wood with highly aligned cellulose nanofibres. This strategy is shown to be universally effective for various species of wood. Our processed wood has a specific strength higher than that of most structural metals and alloys, making it a low-cost, high-performance, lightweight alternative.

Anisotropic, Transparent Films with Aligned Cellulose Nanofibers

Transparent films or substrates are ubiquitously used in photonics and optoelectronics, with glass and plastics as traditional choice of materials. Transparent films made of cellulose nanofibers are reported recently. However, all these films are isotropic in nature. This work, for the first time, reports a remarkably facile and effective approach to fabricating anisotropic transparent films directly from wood. The resulting films exhibit an array of exceptional optical and mechanical properties. The well-aligned cellulose nanofibers in natural wood are maintained during delignification, leading to an anisotropic film with high transparency (≈90% transmittance) and huge intensity ratio of transmitted light up to 350%. The anisotropic film with well-aligned cellulose nanofibers has a mechanical tensile strength of up to 350 MPa, nearly three times of that of a film with randomly distributed cellulose nanofibers. Atomistic mechanics modeling further reveals the dependence of the film mechanical properties on the alignment of cellulose nanofibers through the film thickness direction. This study also demonstrates guided liquid transport in a mesoporous, anisotropic wood film and its possible application in enabling new nanoelectronic devices. These unique and highly desirable properties of the anisotropic transparent film can potentially open up a range of green electronics and nanofluidics.

Nanotube dispersion and polymer conformational confinement in a nanocomposite fiber: a joint computational experimental study.

A combination of computational and experimental methods was implemented to understand and confirm that conformational changes of a polymer [specifically polyacrylonitrile (PAN)] vary with the dispersion quality and confinement between single-wall carbon nanotubes (SWNT) in the composite fibers. A shear-flow gel-spinning approach was utilized to produce PAN-based composite fibers with high concentration (i.e., loading of 10 wt %) of SWNT. Dispersion qualities of SWNT ranging from low to high were identified in the fibers, and their effects on the structural morphologies and mechanical properties of the composites were examined. These results show that, as the SWNT dispersion quality in terms of distribution in the fiber and exfoliation increases, PAN conformations were confined to the extended-chain form. Full atomistic computational results show that the surface interaction energy between isolated PAN and SWNT was not preferred, leading to the self-agglomeration of PAN. However, confinement of the polymer chains between SWNT bundles or individual tubes (i.e., molecular crowding) resulted in large increases in the PAN-SWNT interaction energy. In other words, the crowding of polymer chains by the SWNT at high concentrations can promote extended-chain conformational development during fiber spinning. This was also evidenced experimentally by the observance of significantly improved PAN orientation and crystallization in the composite. Ultimately this work provides fundamental insight toward the specific structural changes capable at the polymer/nanotube interface which are important toward improvement of the effective contribution of the SWNT to the mechanical performance of the composite.

Lysozyme Coated DNA and DNA/SWNT Fibers by Solution Spinning

DNA fibers were prepared by solution spinning of DNA in a lysozyme (LSZ) coagulation/gelation bath. Strong positive charges carried by LSZ protein condensed the DNA (strong negative charged) molecules resulting in self-assembly and the formation of fibrillar structures in a gel-like network. DNA/LSZ fibril formation was found to be dependent on the ratio of DNA to LSZ. A minimum 0.1 wt.-% of LSZ was necessary to condense 0.1 wt.-% of DNA into micro-fibrils. Macroscopic fiber spinning was possible by introducing a 0.1 wt.-% DNA aqueous solution into a 0.2 wt.-% LSZ coagulation bath which resulted in fibers with ≈20 µm diameter. Single-walled carbon nanotubes (SWNT) were also incorporated into these fibers to explore the possibility for creating hybrid materials. All DNA-based fibers exhibit strong birefringence confirming molecular orientation along the fiber axis. Due to the presence of LSZ, the fibers exhibit antimicrobial activity against bacteria like Micrococcus lysodeikticus.

Gel-spinning of mimetic collagen and collagen/nano-carbon fibers: Understanding multi-scale influences on molecular ordering and fibril alignment

Synthetic gel-spun collagen and collagen/nano-carbon fibers were found to exhibit structural mimicry comparable to native tendons. X-ray scattering and microscopy analyses are used to characterize the molecular and fibrillar alignment in the synthetic fibers, where D-banding is observed throughout the spun fibers - consistent with native collagen. For the composite collagen/nano-carbon fibers, the morphology and dispersion quality of the nano-carbons within was found to play a significant role in influencing collagen molecular ordering and fibril alignment. Fibrillar and molecular alignment was also better preserved during elongation of the composites as compared to the control collagen fibers. These results show the structural influence of a rigid inclusion on the collagen fibril structure. Both dry- and wet-state tensile testing were performed on the collagen fibers, and these results show behavior comparable to the native materials. Dry-state tests also reveal interfacial interaction between the nano-fillers and the collagen fibrils through theoretical analysis. Wet-state tensile testing indicates the structure-property behavior of the mimetic hierarchical structure within the synthetic fibers.