Preparation of Polyethylene/α-Zirconium Phosphate Nanocomposites via a Well-Controlled Polyethylene-Grafted Interface.

It is a daunting task to prepare polyolefin nanocomposites that contain well-exfoliated nanoplatelets due to the nonpolar and high crystallinity nature of polyolefins. In this research, a robust approach was developed to prepare polyethylene (PE) nanocomposites by grafting maleated polyethylene (MPE) onto pre-exfoliated α-zirconium phosphate (ZrP) nanoplatelets via a simple amine-anhydride reaction to form ZrP-g-MPE. Several variables, including maleic anhydride (MA) content, MPE graft density, MPE molecular weight, and PE matrix crystallinity, were investigated to determine how they influence ZrP-g-MPE dispersion in PE. It was found that grafted PE has a different morphology and that the long PE brushes with medium graft density on ZrP can achieve sufficient chain entanglement and cocrystallization with PE matrix to stabilize and maintain ZrP-g-MPE dispersion after solution or melt mixing. This leads to enhanced Young's modulus, yield stress, and ductility. The structure-property relationship of PE/ZrP-g-MPE nanocomposites and usefulness of this study for the preparation of high-performance polyolefin nanocomposites are discussed.

Ultrastrong Carbon Nanotubes-Copper Core-Shell Wires with Enhanced Electrical and Thermal Conductivities as High-Performance Power Transmission Cables.

Demands for high-performance electrical power transmission cables continue to rise, especially for offshore power transmission, electric vehicles, portable electronics, and deployable military applications. Carbon nanotubes (CNTs)-Copper (Cu) core-shell wire is regarded as one of the best candidate material systems for transmitting electricity and thermal energy. In this study, a facile and robust approach was developed to enhance the CNT-Cu interfacial interactions. This approach consists of a substrate-enhanced electroless deposition step for Cu pre-seeding and thiol functionalization. Benefiting from the thiol-activated CNT surface and Cu seed deposit, the CNTs-Cu core-shell wire forms a densely packed Cu shell with a void-free CNT-Cu interface. Consequently, the CNTs-Cu core-shell wire possesses (1) superior specific strength (eightfold stronger), (2) 30% higher specific conductivity, (3) 120% higher specific ampacity, and (4) an impressive 110% higher thermal conductivity compared with pure Cu wires. Moreover, this composite wire still maintains its structural integrity and electrical properties over 600 cycles of the fatigue bending test, rendering this system an excellent candidate for high-performance electrical cable and conductor applications.

Fracture Behavior of Polyrotaxane-Toughened Poly(Methyl Methacrylate).

The fracture behavior of polyrotaxane (PR)-modified poly(methyl methacrylate) (PMMA) was investigated. PR is a supramolecule with rings threaded onto a linear backbone chain, which is capped by bulky end groups to prevent the rings from de-threading. The ring structure is α-cyclodextrin (CD), and it can be functionalized to enhance its affinity with the hosting polymer matrix. Adding only 1 wt % of PR containing methacrylate functional groups (mPR) at the terminal of some of the polycaprolactone-grafted chains on CD promotes massive crazing, resulting in a significant improvement in fracture toughness while maintaining the modulus and transparency of the PMMA matrix. Dynamic mechanical analysis and atomic force microscopy studies reveal that mPR strongly interact with PMMA, leading to higher molecular mobility and enhanced molecular cooperativity during deformation. This molecular cooperativity may be responsible for the formation of massive crazing in a PMMA matrix, which leads to greatly improved fracture toughness.

Photopolymerized superhydrophobic hybrid coating enabled by dual-purpose tetrapodal ZnO for liquid/liquid separation.

Low-cost and scalable superhydrophobic coating methods provide viable approaches for energy-efficient separation of immiscible liquid/liquid mixtures. A scalable photopolymerization method is developed to functionalize porous substrates with a hybrid coating of tetrapodal ZnO (T-ZnO) and polymethacrylate, which exhibits simultaneous superhydrophobicity and superoleophilicity. Here, T-ZnO serves dual purposes by (i) initiating radical photopolymerization during the fabrication process through a hole-mediated pathway and (ii) providing a hierarchical surface roughness to amplify wettability characteristics and suspend liquid droplets in the metastable Cassie-Baxter regime. Photopolymerization provides a means to finely control the conversion and spatial distribution of the formed polymer, whilst allowing for facile large-area fabrication and potential coating on heat-sensitive substrates. Coated stainless-steel meshes and filter papers with desired superhydrophobic/superoleophilic properties exhibit excellent performance in separating stratified oil/water, oil/ionic-liquid, and water/ionic-liquid mixtures as well as water-in-oil emulsions. The hybrid coating demonstrates desired mechanical robustness and chemical resistance for their long-term application in large-scale energy-efficient separation of immiscible liquid/liquid mixtures.

Evaluation of 1-dimensional nanomaterials release during electrospinning and thermogravimetric analysis.

The growing research interests with engineered nanomaterials in academic laboratories and manufacturing facilities pose potential safety risks to students and workers. New nanoparticle substances, compositions, and processing approaches are developed regularly, creating new health risks which may not have been addressed previously. Accordingly, the Institute of Occupational Medicine conducted field studies at Texas A&M University (TAMU) to characterize possible particle emissions during processing and fabrication of carbon nanotubes, copper nanowires, and polymeric fibers. The nature of the monitoring work carried out at TAMU was to investigate the potential release of 1D nanomaterials to air from activities associated with synthesis, handling, thermal gravimetric analysis, and electrospinning processes, and evaluate the effectiveness of the utilized control measures. The potential nanoparticle release to air from each activity was investigated using a combination of particle detection instrumentations, coupled with standard filter-based sampling techniques. The analyses indicated that a measurable quantity of free carbon nanosphere aggregates was detected during these activities; however, no free MWCNTs or nanowires were detected. Scanning electron microscopy identified the presence of carbon nanospheres aggregates on the filters. While the control measures used at TAMU are effective in containing the nanomaterial release during processing, poor handling and occupational hygiene practices can increase the risk of employee exposure to the nanomaterials.

Preparation of Well-Exfoliated Poly(ethylene-co-vinyl acetate)/α-Zirconium Phosphate Nanocomposites.

Poly(ethylene-co-vinyl acetate) (PEVAc) nanocomposites containing exfoliated α-zirconium phosphate (ZrP) have been prepared using a simple solution mixing method to improve their barrier and mechanical properties. ZrP was pre-exfoliated with a surfactant, followed by additional targeted surface functionalization and surfactant exchange to allow for hydrogen bonding of ZrP with the acetate functionality on PEVAc and to improve ZrP surface hydrophobicity. The solvent is found to play an important role in stabilizing ZrP exfoliation in the presence of PEVAc to retain full exfoliation and homogeneous dispersion upon the removal of the solvent. The PEVAc/ZrP nanocomposite exhibits greatly improved oxygen barrier, melt strength, and mechanical properties. The usefulness of the present study for the preparation of olefinic polymer nanocomposites is discussed.

Critical challenges and advances in the carbon nanotube-metal interface for next-generation electronics.

Next-generation electronics can no longer solely rely on conventional materials; miniaturization of portable electronics is pushing Si-based semiconductors and metallic conductors to their operational limits, flexible displays will make common conductive metal oxide materials obsolete, and weight reduction requirement in the aerospace industry demands scientists to seek reliable low-density conductors. Excellent electrical and mechanical properties, coupled with low density, make carbon nanotubes (CNTs) attractive candidates for future electronics. However, translating these remarkable properties into commercial macroscale applications has been disappointing. To fully realize their great potential, CNTs need to be seamlessly incorporated into metallic structures or have to synergistically work alongside them which is still challenging. Here, we review the major challenges in CNT-metal systems that impede their application in electronic devices and highlight significant breakthroughs. A few key applications that can capitalize on CNT-metal structures are also discussed. We specifically focus on the interfacial interaction and materials science aspects of CNT-metal structures.

Manipulation of Fracture Behavior of Poly(methyl methacrylate) Nanocomposites by Interfacial Design of a Metal-Organic-Framework Nanoparticle Toughener.

The interfacial region between nanoparticles and polymer matrix plays a critical role in influencing the mechanical behavior of polymer nanocomposites. In this work, a set of model systems based on poly(methyl methacrylate) (PMMA) matrix containing poly(alkyl glycidyl ether) brushes grafted on 50 nm metal-organic-framework (MOF) nanoparticles were synthesized and investigated. By systematically increasing the polymer brush length and graft density on the MOF nanoparticles, the fracture behavior of PMMA/MOF nanocomposite changes from forming only a few large crazes to generating massive crazing and to undergoing shear banding, which results in significant improvement in fracture toughness. The implication of the present finding for the interfacial design of the nanoparticles for the development of high-performance, multifunctional polymer nanocomposites is discussed.

α-Zirconium Phosphate Nanoplatelets with Covalent Modifiers for Exfoliation in Organic Media.

Nanocomposites with exfoliated 2D materials are highly sought after due to resulting material enhancement of barrier and increased modulus among others. In the past, this was achieved by using polyols that were effective but caused a significant drop in the glass transition temperature of the nanocomposite. In this contribution, α-zirconium phosphate (ZrP) nanoplatelets were covalently modified to allow for dispersion in solvents with varying hydrophobicity and poly(methyl methacrylate) (PMMA) for the first time. The nanoplatelets were prepared by using a polyetheramine surfactant to achieve exfoliation, followed by modification with epoxides. Combinations of different epoxides were shown capable of tuning the functionality and hydrophobicity of the exfoliated ZrP in organic media. After grafting glycidyl methacrylate and cyclohexene oxide to the surface of ZrP, an in situ free radical polymerization of MMA allowed for high concentrations of self-assembled exfoliated ZrP in a PMMA matrix.

Copper(I)-alkylamine mediated synthesis of copper nanowires.

Formation of a Cu(i)-alkylamine complex is found to be the key step for Cu(ii) ions to reduce to Cu(0) in the presence of glucose. Also, alkylamines in Cu nanowire synthesis serve triple roles as a reducing, complexation and capping agent. Alkylamines reduce Cu(ii) to Cu(i) at above 100 °C and protect the Cu(i) by forming a Cu ion-alkylamine coordination complex with a 1 : 2 ratio in an aqueous solution. With respect to the 1 : 2 complex ratio, the additional free alkylamines ensure a stable Cu(i)-alkylamine complex. After completion of Cu(i)-Cu(0) reduction by glucose, alkylamines remain on Cu(0) seeds to regulate the anisotropic growth of Cu nanocrystals. Long-chain (≥C16) alkylamines are found to help produce high-quality Cu nanowires, while short-chain (≤C12) alkylamines only produce CuO products. Furthermore, Cu nanowire synthesis is found to be sensitive to additional chemicals as they may destabilize Cu ion-alkylamine complexes. By comparing the Cu(i)-alkylamine and Maillard reaction mediated mechanism, the complete Cu nanowire synthesis process using glucose is revealed.

Modulation versus Templating: Fine-Tuning of Hierarchally Porous PCN-250 Using Fatty Acids To Engineer Guest Adsorption.

Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal-organic frameworks (HP-MOFs). In this study, by using fatty acids with different lengths and concentrations as dual-functional modulators/templates, we were able to obtain HP-MOFs with tunable mesopores that exhibit different pore diameters and locations. We found that the length and concentration of the fatty acids can determine if micelle formation occurs, which in turn dictates the porosity of the resulting HP-MOFs. The HP-MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure-performance relationships were ascribed to the pore diameters and locations. This approach could provide a potentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.

Non-Solvent Fractionation of Lignin Enhances Carbon Fiber Performance.

Even though lignin carbon fiber has been sought after for several decades, the poor mechanical performance remains to be a major barrier for commercial applications. The low mechanical performance is attributed to the heterogeneity of lignin polymer. Recent advances in fractionation technologies showed the great potential to reduce lignin heterogeneity, but current fractionation methods often depend on costly chemicals and materials such as enzymes, organic solvents, membranes, and dialysis tubes. Here, a new non-solvent strategy was developed to fractionate lignin by autohydrolysis. By using only water, lignin was efficiently fractionated into water-soluble and -insoluble fractions. The latter fraction had increased molecular weight and uniformity and resulted in more ß-O-4 interunitary linkages as analyzed by size-exclusion chromatography and 2D heteronuclear single quantum coherence NMR spectroscopy, respectively. In particular, the water-insoluble fraction significantly enhanced the mechanical performances of the resultant carbon fibers. Mechanistic study by differential scanning calorimetry (DSC) revealed that the miscibility of lignin with guest polyacrylonitrile molecules was improved with the reduced lignin heterogeneity. Crystallite analyses by XRD and Raman spectroscopy revealed that the crystallite size and content of the pre-graphitic turbostratic carbon structure were increased. The fundamental understanding revealed how lignin fractionation could modify lignin chemical features to enhance the mechanical performance of resultant carbon fibers. The autohydrolysis fractionation thus represents a green, economic, and efficient methodology to process lignin waste and boost lignin carbon fiber quality, which could open new horizons for lignin valorization.

Porous SnO2-Cu x O nanocomposite thin film on carbon nanotubes as electrodes for high performance supercapacitors.

Metal oxides are promising materials for supercapacitors due to their high theoretical capacitance. However, their poor electrical conductivity is a major challenge. Hybridization with conductive nanostructured carbon-based materials such as carbon nanotubes (CNTs) has been proposed to improve the conductivity and increase the surface area. In this work, CNTs are used as a template for synthesizing porous thin films of SnO2-CuO-Cu2O (SnO2-Cu x O) via an electroless deposition technique. Tin, with its high wettability and electrical conductivity, acts as an intermediate layer between copper and the CNTs and provides a strong interaction between them. We also observed that by controlling the interfacial characteristics of CNTs and varying the composition of the electroless bath, the SnO2-Cu x O thin film morphology can be easily manipulated. Electrochemical characterizations show that CNT/SnO2-Cu x O nanocomposite possesses pseudocapacitive behavior that reaches a specific capacitance of 662 F g-1 and the retention is 94% after 5000 cycles, which outperforms any known copper and tin-based supercapacitors in the literature. This excellent performance is mainly attributed to high specific surface area, small particle size, the synergistic effect of Sn, and conductivity improvement by using CNTs. The combination of CNTs and metal oxides holds promise for supercapacitors with improved performance.

Epoxy Nanocomposites Containing Zeolitic Imidazolate Framework-8.

Zeolitic imidazole framework-8 (ZIF-8) is utilized as a functional filler and a curing agent in the preparation of epoxy nanocomposites. The imidazole group on the surface of the ZIF-8 initiates epoxy curing, resulting in covalent bonding between the ZIF-8 crystals and epoxy matrix. A substantial reduction in dielectric constant and increase in tensile modulus were observed. The implication of the present study for utilization of metal-organic framework to improve physical and mechanical properties of polymeric matrixes is discussed.

1D copper nanowires for flexible printable electronics and high ampacity wires.

This paper addresses the synthesis and a detailed electrical analysis of individual copper nanowires (CuNWs). One dimensional CuNWs are chemically grown using bromide ions (Br-) as a co-capping agent. By partially replacing alkyl amines with Br-, the isotropic growth on Cu seeds was suppressed during the synthesis. To study the electrical properties of individual CuNWs, a fabrication method is developed which does not require any e-beam lithography process. Chemically grown CuNWs have an ampacity of about 30 million amps per cm2, which is more than one order of magnitude larger than bulk Cu. These good quality, easy to synthesize CuNWs are excellent candidates for creating high ampacity wires and flexible printable electronics.

Interfacial Phenomena and Mechanical Behavior of Polyetheretherketone/Polybenzimidazole Blend under Hygrothermal Environment.

Demands for engineering applications of high performance polymers, such as the polyaryletherketone families, have grown significantly in recent years. Fundamental knowledge on the mechanical behavior of such polymers, especially under harsh environments, is still lacking. In this study, the mechanical behavior and interfacial phenomena of a blend of polybenzimidazole (PBI) particles having sizes of about 50 µm and polyetheretherketone (PEEK) matrix at 50:50 weight ratio was characterized. PBI and PEEK are known to be incompatible with each other in the dry state. The possible influence of hygrothermal exposure on interfacial bonding between PEEK and PBI has been systematically studied. Under dry conditions, the PEEK matrix dominates the dynamic mechanical behavior, indicating no noticeable viscoelastic coupling between the two phases. After being exposed to hygrothermal conditions, the Tg of the PEEK phase in the blend shifts to a lower temperature by as much as 26 °C. The extent of this shift is much greater than what is observed for neat PEEK alone under the same condition. Nanomechanical property mapping results indicate that the interfacial region is broadened after 288 °C hot water immersion treatment. The above finding strongly suggests the hygrothermal conditioning promotes apparent compatibility between PEEK and PBI. Likewise, the fracture behavior of the blend provides direct evidence that the interfacial adhesion is greater than the cohesive strength of either phase after water immersion. In the meantime, it is found that both fracture toughness and tensile strength of the blend are improved by water absorption at 60 °C, at the expense of a minor reduction in Young's modulus. However, if the blend is exposed to hot water at 288 °C, all of the mechanical properties will deteriorate significantly. The possible causes of the mechanical property deterioration in the PEEK/PBI blend after hygrothermal treatment are discussed.

Solution-Processable Core-Extended Quinacridone Derivatives with Intact Hydrogen Bonds.

A highly efficient and feasible "condensation followed by annulation" synthetic approach was developed to afford a subset of 9-ring-fused quinacridone derivatives on a 10 g scale. Despite the amenable intermolecular hydrogen-bonding ability of these rigid molecules, good solubility in common organic solvents and solution processability into uniformed thin films were achieved. Integrated advantages in the synthesis and properties make these compounds ideal building blocks for high-performance dyes and optoelectronic materials.

The Effect of Surface Chemistry on the Glass Transition of Polycarbonate Inside Cylindrical Nanopores.

The effect of surface chemistry on the glass transition of polycarbonate (PC) inside cylindrical nanopores is studied. Polycarbonate is melt-wetted into nanoporous anodic aluminum oxide (AAO) treated with hydrophobic alkyl- and fluorosilanes of varying length. The curvature observed at the nanowire tips is consistent with a contact angle descriptive of polycarbonate-AAO surface interactions. Differential scanning calorimetry (DSC) thermograms reveal a distinct broadening of the Tg that is related to the motion of polymer chains at the nanopore wall as well as at the core. DSC and thermal gravimetric analysis (TGA) show that polycarbonate infiltrated into a naked AAO template (without silane treatment) degrades upon heating, suggestive of a surface-catalyzed degradation mechanism. It is further shown that silane treatment largely prevents PC thermal degradation.

Mechanical reinforcement of epoxy with self-assembled synthetic clay in smectic order.

Epoxy films containing self-assembled 2D colloidal α-zirconium phosphate nanoplatelets (ZrP) in smectic order were prepared using a simple, energy-efficient fabrication process suitable to industrial processing. The ZrP nanoplatelets form a chiral smectic mesophase with simultaneous lamellar order and helical arrangements in epoxy. The epoxy nanocomposite films are transparent and flexible and exhibit exceptionally high tensile modulus and strength. The findings have broad implications for development of multifunctional materials for engineering applications.

Large-scale self-assembled zirconium phosphate smectic layers via a simple spray-coating process.

The large-scale assembly of asymmetric colloidal particles is used in creating high-performance fibres. A similar concept is extended to the manufacturing of thin films of self-assembled two-dimensional crystal-type materials with enhanced and tunable properties. Here we present a spray-coating method to manufacture thin, flexible and transparent epoxy films containing zirconium phosphate nanoplatelets self-assembled into a lamellar arrangement aligned parallel to the substrate. The self-assembled mesophase of zirconium phosphate nanoplatelets is stabilized by epoxy pre-polymer and exhibits rheology favourable towards large-scale manufacturing. The thermally cured film forms a mechanically robust coating and shows excellent gas barrier properties at both low- and high humidity levels as a result of the highly aligned and overlapping arrangement of nanoplatelets. This work shows that the large-scale ordering of high aspect ratio nanoplatelets is easier to achieve than previously thought and may have implications in the technological applications for similar materials.