Sustainable barrier paper coating based on alpha-1,3 glucan and natural rubber latex.

There is an increasing interest in utilizing more sustainable and inherently biodegradable materials alternatives ideally derived from renewable resources for modern material applications, especially in the area of packaging materials. This work employed the polysaccharide alpha-1,3-glucan derived from an enzymatic polymerization process as a functional additive for natural rubber (NR) latex-based coating films. Coating formulations containing NR and 9-50 wt% alpha-1,3 glucan were prepared and then applied to paper substrates at different thicknesses. The effect of coating formulations on the barrier properties (e.g., oxygen, oil, water vapor barrier), the viscosity, and dry and wet tensile properties were investigated. The NR/glucan coatings exhibited outstanding tensile properties and balanced oxygen and oil barrier performance. However, higher glucan loading could be detrimental to moisture barrier. Overall, this study indicated that the NR/glucan coating films are comparable in performance to commercial coating formulations while providing a renewable, potential to be recycled with paper, and biodegradable alternative.

High-Solids, Solvent-Free Modification of Engineered Polysaccharides.

The nature-identical engineered polysaccharide α-(1,3) glucan, produced by the enzymatic polymerization of sucrose, was chemically modified by acylation with succinic anhydride. This modification reaction was initially performed at the micro scale in a TGA reactor to access a range of reaction conditions and to study the mechanism of the reaction. Subsequently, the best performing conditions were reproduced at the larger laboratory scale. The reaction products were characterized via coupled TGA/DSC analysis, FT-IR spectroscopy, solution viscosity and pH determination. The acylation path resulted in partially modifying the polysaccharide by altering its behavior in terms of thermal properties and solubility. The acylation in a solvent-free approach was found promising for the development of novel, potentially melt-processable and fully bio-based and biodegradable ester compounds.

Elucidating the effect of enzymatic polymerized polysaccharide particle morphology on emulsion properties.

Exploiting the shape of Pickering stabilizers offers the ability to unlock the full potential of nanoparticle-stabilized emulsions for applications in enhanced oil recovery, pharmaceuticals, cosmetics, and coatings. In this work, we utilize engineered polysaccharide particles derived from the enzymatic polymerization of glucose from sucrose with controlled shape for the stabilization of dodecane-in-water emulsions. Altering the particle shape (spherical aggregates, fibrids, or platelets), while maintaining a neutral surface charge allows for a systematic examination of the role of particle shape in the stabilization of emulsions. We find that platelet-shaped particles reduce the interfacial tension and result in the smallest droplet size, while emulsions stabilized by aggregates and fibrids are governed by a network of particles in the continuous phase. Exploiting the synergy between these particles allowed for the tuning of their microstructure and rheological signature which allows us to map and tailor these emulsions for a wider variety of applications.

Enzymatic polymerization derived engineered polysaccharides as reinforcing fillers of ethylene vinyl acetate composites.

A novel monomer based, controlled enzymatic polymerization was employed to produce an engineered alpha-1,3 glucan polysaccharide. The structure and material properties of the engineered polysaccharide were characterized using various techniques. The use of such engineered polysaccharide as a reinforcing filler of polymers was evaluated using model polymers. For this, the alpha-1,3 glucan was incorporated into ethylene vinyl acetate co-polymer (EVA) matrices with vinyl acetate content of 32% and 40% via a melt processing fabrication process. Various mechanical and rheological properties of the fabricated composites were evaluated. The effect of vinyl acetate content of the EVA resin on the interaction with alpha-1,3 glucan that result in various performances attributes was also investigated and reported. The incorporation of alpha-1,3 glucan in these EVA composites resulted in the improvement of key composite properties, such as toughness, modulus, wear resistance, and hardness showing the reinforcing potential of these engineered polysaccharides.

Coarse-grained molecular dynamics simulations of α-1,3-glucan.

In this paper we present a computational study of aggregation in aqueous solutions of α-1,3-glucan captured using a coarse-grained (CG) model that can be extended to other polysaccharides. This CG model captures atomistic geometry (i.e., relative placement of the hydrogen bonding donors and acceptors within the monomer) of the α-1,3-glucan monomer, the directional interactions due to the donor-acceptor hydrogen bonds, and their effect on aggregation of multiple α-1,3-glucan chains without the extensive computational resources needed for simulations with atomistic models. Using this CG model, we conduct molecular dynamics simulations to assess the effect of varying α-1,3-glucan chain length and hydrogen bond interaction strengths on the aggregation of multiple chains at finite concentrations in implicit solvent. We quantify the hydrogen bonding strength needed for multiple chains to aggregate, the distribution of inter- and intra-chain hydrogen bonds within the aggregate and in some cases, the shapes of the aggregate. We also explore the effect of substitution/silencing of some randomly selected or specific hydrogen bonding sites in the chain on the aggregation and aggregate structure. In the unmodified α-1,3-glucan solution, the inter-chain hydrogen bonds cause the chains to aggregate into sheets. Random silencing of hydrogen bonding donor sites only increases the hydrogen bond strength needed for aggregation but retains the same aggregate structure as the unmodified chains. Specific silencing of the hydrogen-bonding site on the C6 carbon leads to the chains aggregating into planar sheets that then fold over to form hollow cylinders at intermediate hydrogen bond strength - 4.7 to 5.3 kcal mol-1. These cylindrical aggregates assemble end-to-end to form larger aggregates at higher hydrogen bond strengths.

Influence of Carbon Nanotube Characteristics on Macroscopic Fiber Properties.

We study how intrinsic parameters of carbon nanotube (CNT) samples affect the properties of macroscopic CNT fibers with optimized structure. We measure CNT diameter, number of walls, aspect ratio, graphitic character, and purity (residual catalyst and non-CNT carbon) in samples from 19 suppliers; we process the highest quality CNT samples into aligned, densely packed fibers, by using an established wet-spinning solution process. We find that fiber properties are mainly controlled by CNT aspect ratio and that sample purity is important for effective spinning. Properties appear largely unaffected by CNT diameter, number of walls, and graphitic character (determined by Raman G/D ratio) as long as the fibers comprise thin few-walled CNTs with high G/D ratio (above ∼20). We show that both strength and conductivity can be improved simultaneously by assembling high aspect ratio CNTs, producing continuous CNT fibers with an average tensile strength of 2.4 GPa and a room temperature electrical conductivity of 8.5 MS/m, ∼2 times higher than the highest reported literature value (∼15% of copper's value), obtained without postspinning doping. This understanding of the relationship of intrinsic CNT parameters to macroscopic fiber properties is key to guiding CNT synthesis and continued improvement of fiber properties, paving the way for CNT fiber introduction in large-scale aerospace, consumer electronics, and textile applications.

Direct Imaging of Carbon Nanotube Liquid-Crystalline Phase Development in True Solutions.

Using direct-imaging cryogenic transmission and scanning electron microscopy, we show different stages of liquid-crystalline phase development in progressively more concentrated solutions of carbon nanotubes in chlorosulfonic acid: a dilute phase of individually dissolved carbon nanotubes; semidilute and concentrated isotropic phases; coexisting concentrated isotropic and nematic phases in local equilibrium with each other; and a fully liquid-crystalline phase. Nanometric resolution of cryogenic electron microscopy reveals carbon nanotube self-assembly into liquid-crystalline domains of several nanometers in width at very early stages. We find significant differences in carbon nanotube liquid-crystalline domain morphology as a function of the carbon nanotube aspect ratio, diameter, and degree of purity.

Experimental realization of crossover in shape and director field of nematic tactoids.

Spindle-shaped nematic droplets (tactoids) form in solutions of rod-like molecules at the onset of the liquid crystalline phase. Their unique shape and internal structure result from the interplay of the elastic deformation of the nematic and anisotropic surface forces. The balance of these forces dictates that tactoids must display a continuous variation in aspect ratio and director-field configuration. Yet, such continuous transition has eluded observation for decades: tactoids have displayed either a bipolar configuration with particles aligned parallel to the droplet interface or a homogeneous configuration with particles aligned parallel to the long axis of the tactoid. Here, we report the first observation of the continuous transition in shape and director-field configuration of tactoids in true solutions of carbon nanotubes in chlorosulfonic acid. This observation is possible because the exceptional length of carbon nanotubes shifts the transition to a size range that can be visualized by optical microscopy. Polarization micrographs yield the interfacial and elastic properties of the system. Absorbance anisotropy measurements provide the highest nematic order parameter (S=0.79) measured to date for a nematic phase of carbon nanotubes at coexistence with its isotropic phase.

Three-dimensional patterning of solid microstructures through laser reduction of colloidal graphene oxide in liquid-crystalline dispersions.

Graphene materials and structures have become an essential part of modern electronics and photovoltaics. However, despite many production methods, applications of graphene-based structures are hindered by high costs, lack of scalability and limitations in spatial patterning. Here we fabricate three-dimensional functional solid microstructures of reduced graphene oxide in a lyotropic nematic liquid crystal of graphene oxide flakes using a pulsed near-infrared laser. This reliable, scalable approach is mask-free, does not require special chemical reduction agents, and can be implemented at ambient conditions starting from aqueous graphene oxide flakes. Orientational ordering of graphene oxide flakes in self-assembled liquid-crystalline phases enables laser patterning of complex, three-dimensional reduced graphene oxide structures and colloidal particles, such as trefoil knots, with 'frozen' orientational order of flakes. These structures and particles are mechanically rigid and range from hundreds of nanometres to millimetres in size, as needed for applications in colloids, electronics, photonics and display technology.

Statistical length measurement method by direct imaging of carbon nanotubes.

The influence of carbon nanotube (CNT) length on their macroscopic properties requires an accurate methodology for CNT length measurement. So far, existing techniques are limited to short (less than a few micrometers) CNTs and sample preparation methods that bias the measured values. Here, we show that the average length of carbon nanotubes (CNTs) can be measured by cryogenic transmission electron microscopy (cryo-TEM) of CNTs in chlorosulfonic acid. The method consists of dissolving at low concentration CNTs in chlorosulfonic acid (a true solvent), imaging the individual CNTs by cryo-TEM, and processing and analyzing the images to determine CNT length. By measuring the total CNT contour length and number of CNT ends in each image, and by applying statistical analysis, we extend the method to cases where each CNT is long enough to span many cryo-TEM images, making the direct length measurement of an entire CNT impractical. Hence, this new technique can be used effectively to estimate samples in a wide range of CNT lengths, although we find that cryo-TEM imaging may bias the measurement towards longer CNTs, which are easier to detect. Our statistical method is also applied to AFM images of CNTs to show that, by using only a few AFM images, it yields estimates that are consistent with literature techniques, based on individually measuring a higher number of CNTs.

Direct real-time monitoring of stage transitions in graphite intercalation compounds.

Graphite intercalation compounds (GIC) possess a broad range of unique properties that are not specific to the parent materials. While the stage transition, changing the number of graphene layers sandwiched between the two layers of intercalant, is fundamentally important and has been theoretically addressed, experimental studies revealed only macroscopic parameters. On the microscale, the phenomenon remains elusive up to the present day. Here we monitor directly in real time the stage transitions using a combination of optical microscopy and Raman spectroscopy. These direct observations yield several mechanistic conclusions. While we obtained strong experimental evidence in support of the Daumas-Herold theory, we find that the conventional interpretation of stage transitions as sliding of the existing intercalant domains does not sufficiently capture the actual phenomena. The entire GIC structure transforms considerably during the stage transition. Among other observations, massive wavefront-like perturbations occur on the graphite surface, which we term the tidal wave effect.

Strong, light, multifunctional fibers of carbon nanotubes with ultrahigh conductivity.

Broader applications of carbon nanotubes to real-world problems have largely gone unfulfilled because of difficult material synthesis and laborious processing. We report high-performance multifunctional carbon nanotube (CNT) fibers that combine the specific strength, stiffness, and thermal conductivity of carbon fibers with the specific electrical conductivity of metals. These fibers consist of bulk-grown CNTs and are produced by high-throughput wet spinning, the same process used to produce high-performance industrial fibers. These scalable CNT fibers are positioned for high-value applications, such as aerospace electronics and field emission, and can evolve into engineered materials with broad long-term impact, from consumer electronics to long-range power transmission.

Graphene nanoribbons as an advanced precursor for making carbon fiber.

Graphene oxide nanoribbons (GONRs) and chemically reduced graphene nanoribbons (crGNRs) were dispersed at high concentrations in chlorosulfonic acid to form anisotropic liquid crystal phases. The liquid crystal solutions were spun directly into hundreds of meters of continuous macroscopic fibers. The relationship of fiber morphology to coagulation bath conditions was studied. The effects of colloid concentration, annealing temperature, spinning air gap, and pretension during annealing on the fibers' performance were also investigated. Heat treatment of the as-spun GONR fibers at 1500 °C produced thermally reduced graphene nanoribbon (trGNR) fibers with a tensile strength of 378 MPa, Young's modulus of 36.2 GPa, and electrical conductivity of 285 S/cm, which is considerably higher than that in other reported graphene-derived fibers. This better trGNR fiber performance was due to the air gap spinning and annealing with pretension that produced higher molecular alignment within the fibers, as determined by X-ray diffraction and scanning electron microscopy. The specific modulus of trGNR fibers is higher than that of the commercial general purpose carbon fibers and commonly used metals such as Al, Cu, and steel. The properties of trGNR fibers can be further improved by optimizing the spinning conditions with higher draw ratio, annealing conditions with higher pretensions, and using longer flake GONRs. This technique is a new high-carbon-yield approach to make the next generation carbon fibers based on solution-based liquid crystal phase spinning.

High-performance carbon nanotube transparent conductive films by scalable dip coating.

Transparent conductive carbon nanotube (CNT) films were fabricated by dip-coating solutions of pristine CNTs dissolved in chlorosulfonic acid (CSA) and then removing the CSA. The film performance and morphology (including alignment) were controlled by the CNT length, solution concentration, coating speed, and level of doping. Using long CNTs (∼10 µm), uniform films were produced with excellent optoelectrical performance (∼100 Ω/sq sheet resistance at ∼90% transmittance in the visible), in the range of applied interest for touch screens and flexible electronics. This technique has potential for commercialization because it preserves the length and quality of the CNTs (leading to enhanced film performance) and operates at high CNT concentration and coating speed without using surfactants (decreasing production costs).

Nonlinear photoluminescence imaging of isotropic and liquid crystalline dispersions of graphene oxide.

We report a visible-range nonlinear photoluminescence (PL) from graphene oxide (GO) flakes excited by near-infrared femtosecond laser light. PL intensity has nonlinear dependence on the laser power, implying a multiphoton excitation process, and also strongly depends on a linear polarization orientation of excitation light, being at maximum when it is parallel to flakes. We show that PL can be used for a fully three-dimensional label-free imaging of isotropic, nematic, and lamellar liquid crystalline dispersions of GO flakes in water. This nonlinear PL is of interest for applications in direct label-free imaging of composite materials and study of orientational ordering in mesomorphic phases formed by these flakes, as well as in biomedical and sensing applications utilizing GO.

Overcoming the "coffee-stain" effect by compositional Marangoni-flow-assisted drop-drying.

Attempts at depositing uniform films of nanoparticles by drop-drying have been frustrated by the "coffee-stain" effect due to convective macroscopic flow into the contact line. Here, we show that uniform deposition of nanoparticles in aqueous suspensions can be attained easily by drying the droplet in an ethanol vapor atmosphere. This technique allows the particle-laden water droplets to spread on a variety of surfaces such as glass, silicon, mica, PDMS, and even Teflon. Visualization of droplet shape and internal flow shows initial droplet spreading and strong recirculating flow during spreading and shrinkage. The initial spreading is due to a diminishing contact angle from the absorption of ethanol from the vapor at the contact line. During the drying phase, the vapor is saturated in ethanol, leading to preferential evaporation of water at the contact line. This generates a surface tension gradient that drives a strong recirculating flow and homogenizes the nanoparticle concentration. We show that this method can be used for depositing catalyst nanoparticles for the growth of single-walled carbon nanotubes as well as to manufacture plasmonic films of well-spaced, unaggregated gold nanoparticles.

Direct imaging of carbon nanotubes spontaneously filled with solvent.

For the first time, cryo-TEM imaging is used to directly show spontaneous filling of carbon nanotubes immersed in a solvent in the native state at ambient conditions. Multi-walled carbon nanotubes are dissolved in chlorosulfonic acid, and the high contrast between the acid and the carbon shows the difference between filled and unfilled nanotubes.

Spontaneous dissolution of ultralong single- and multiwalled carbon nanotubes.

We report that chlorosulfonic acid is a true solvent for a wide range of carbon nanotubes (CNTs), including single-walled (SWNTs), double-walled (DWNTs), multiwalled carbon nanotubes (MWNTs), and CNTs hundreds of micrometers long. The CNTs dissolve as individuals at low concentrations, as determined by cryo-TEM (cryogenic transmission electron microscopy), and form liquid-crystalline phases at high concentrations. The mechanism of dissolution is electrostatic stabilization through reversible protonation of the CNT side walls, as previously established for SWNTs. CNTs with highly defective side walls do not protonate sufficiently and, hence, do not dissolve. The dissolution and liquid-crystallinity of ultralong CNTs are critical advances in the liquid-phase processing of macroscopic CNT-based materials, such as fibers and films.

Diameter-dependent solubility of single-walled carbon nanotubes.

We study the solubility and dispersibility of as-produced and purified HiPco single-walled carbon nanotubes (SWNTs). Variation in specific operating conditions of the HiPco process are found to lead to significant differences in the respective SWNT solubilities in oleum and surfactant suspensions. The diameter distributions of SWNTs dispersed in surfactant solutions are batch-dependent, as evidenced by luminescence and Raman spectroscopies, but are identical for metallic and semiconducting SWNTs within a batch. We thus find that small diameter SWNTs disperse at higher concentration in aqueous surfactants and dissolve at higher concentration in oleum than do large-diameter SWNTs. These results highlight the importance of controlling SWNT synthesis methods in order to optimize processes dependent on solubility, including macroscopic processing such as fiber spinning, material reinforcement, and films production, as well as for fundamental research in type selective chemistry, optoelectronics, and nanophotonics.

Spontaneous high-concentration dispersions and liquid crystals of graphene.

Graphene combines unique electronic properties and surprising quantum effects with outstanding thermal and mechanical properties. Many potential applications, including electronics and nanocomposites, require that graphene be dispersed and processed in a fluid phase. Here, we show that graphite spontaneously exfoliates into single-layer graphene in chlorosulphonic acid, and dissolves at isotropic concentrations as high as approximately 2 mg ml(-1), which is an order of magnitude higher than previously reported values. This occurs without the need for covalent functionalization, surfactant stabilization, or sonication, which can compromise the properties of graphene or reduce flake size. We also report spontaneous formation of liquid-crystalline phases at high concentrations ( approximately 20-30 mg ml(-1)). Transparent, conducting films are produced from these dispersions at 1,000 Omega square(-1) and approximately 80% transparency. High-concentration solutions, both isotropic and liquid crystalline, could be particularly useful for making flexible electronics as well as multifunctional fibres.