Improved Interfacial Bonding Strength and Reliability of Functionalized Graphene Oxide for Cement Reinforcement Applications.

Poor bonding strength between nanomaterials and cement composites inevitably lead to the failure of reinforcement. Herein, a novel functionalization method for the fabrication of functionalized graphene oxide (FGO), which is capable of forming highly reliable covalent bonds with cement hydration products, and therefore, suitable for use as an efficient reinforcing agent for cement composites, is discussed. The bonding strength between cement and aggregates was improved more than 21 times with the reinforcement of FGO. The fabricated FGO also demonstrated many important features, including high reliability in cement pastes, good dispersibility, and efficient structural refinement of cement hydration products. With the incorporation of FGO, cement mortar samples demonstrated up to 40 % increased early and ultimate strength. Such results make the fast demolding and manufacture of light constructions become highly possible, and show strong advantages on improving productivity, saving cost, and reducing CO2 emissions in practical applications.

Multiple growth of graphene from a pre-dissolved carbon source.

Mono- to few-layer graphene materials are successfully synthesized multiple times using Cu-Ni alloy as a catalyst after a single-chemical vapor deposition (CVD) process. The multiple synthesis is realized by extracting carbon source pre-dissolved in the catalyst substrate. Firstly, graphene is grown by the CVD method on Cu-Ni catalyst substrates. Secondly, the same Cu-Nicatalyst foils are annealed, in absence of any external carbon precursor, to grow graphene using the carbon atoms pre-dissolved in the catalyst during the CVD process. This annealing process is repeated to synthesize graphene successfully until carbon is exhausted in the Cu-Ni foils. After the CVD growth and each annealing growth process, the as-grown graphene is removed using a bubbling transfer method. A wide range of characterizations are performed to examine the quality of the obtained graphene material and to monitor the carbon concentration in the catalyst substrates. Results show that graphene from each annealing growth process possesses a similar quality, which confirmed the good reproducibility of the method. This technique brings great freedom to graphene growth and applications, and it could be also used for other 2D material synthesis.

Effects of high temperature treatment of carbon nanotube arrays on graphite: increased crystallinity, anchoring and inter-tube bonding.

Thermal treatment of carbon nanotubes (CNTs) can significantly improve their mechanical, electrical and thermal properties due to reduced defects and increased crystallinity. In this work we investigate the effect of annealing at 3000 °C of vertically aligned CNT arrays synthesized by chemical vapor deposition (CVD) on graphite. Raman measurements show a drastically reduced amount of defects and, together with transmission electron microscope (TEM) diffraction measurements, an increased average crystallite size of around 50%, which corresponds to a 124% increase in Young's modulus. We also find a tendency for CNTs to bond to each other with van der Waals (vdW) forces, which causes individual CNTs to closely align with each other. This bonding causes a densification effect on the entire CNT array, which appears at temperatures >1000 °C. The densification onset temperature corresponds to the thermal decomposition of oxygen containing functional groups, which otherwise prevents close enough contact for vdW bonding. Finally, the remaining CVD catalyst on the bottom of the CNT array is evaporated during annealing, enabling direct anchoring of the CNTs to the underlying graphite substrate.

High porosity and light weight graphene foam heat sink and phase change material container for thermal management.

During the last decade, graphene foam emerged as a promising high porosity 3-dimensional (3D) structure for various applications. More specifically, it has attracted significant interest as a solution for thermal management in electronics. In this study, we investigate the possibility to use such porous materials as a heat sink and a container for a phase change material (PCM). Graphene foam (GF) was produced using chemical vapor deposition (CVD) process and attached to a thermal test chip using sintered silver nanoparticles (Ag NPs). The thermal conductivity of the graphene foam reached 1.3 W m-1 K-1, while the addition of Ag as a graphene foam silver composite (GF/Ag) enhanced further its effective thermal conductivity by 54%. Comparatively to nickel foam, GF and GF/Ag showed lower junction temperatures thanks to higher effective thermal conductivity and a better contact. A finite element model was developed to simulate the fluid flow through the foam structure model and showed a positive and a non-negligible contributions of the secondary microchannel within the graphene foam. A ratio of 15 times was found between the convective heat flux within the primary and secondary microchannel. Our paper successfully demonstrates the possibility of using such 3D porous material as a PCM container and heat sink and highlight the advantage of using the carbon-based high porosity material to take advantage of its additional secondary porosity.

Synthesis of graphene quantum dots and their applications in drug delivery.

This review focuses on the recent advances in the synthesis of graphene quantum dots (GQDs) and their applications in drug delivery. To give a brief understanding about the preparation of GQDs, recent advances in methods of GQDs synthesis are first presented. Afterwards, various drug delivery-release modes of GQDs-based drug delivery systems such as EPR-pH delivery-release mode, ligand-pH delivery-release mode, EPR-Photothermal delivery-Release mode, and Core/Shell-photothermal/magnetic thermal delivery-release mode are reviewed. Finally, the current challenges and the prospective application of GQDs in drug delivery are discussed.

Tailoring the Thermal and Mechanical Properties of Graphene Film by Structural Engineering.

Due to substantial phonon scattering induced by various structural defects, the in-plane thermal conductivity (K) of graphene films (GFs) is still inferior to the commercial pyrolytic graphite sheet (PGS). Here, the problem is solved by engineering the structures of GFs in the aspects of grain size, film alignment, and thickness, and interlayer binding energy. The maximum K of GFs reaches to 3200 W m-1 K-1 and outperforms PGS by 60%. The superior K of GFs is strongly related to its large and intact grains, which are over four times larger than the best PGS. The large smooth features about 11 µm and good layer alignment of GFs also benefit on reducing phonon scattering induced by wrinkles/defects. In addition, the presence of substantial turbostratic-stacking graphene is found up to 37% in thin GFs. The lacking of order in turbostratic-stacking graphene leads to very weak interlayer binding energy, which can significantly decrease the phonon interfacial scattering. The GFs also demonstrate excellent flexibility and high tensile strength, which is about three times higher than PGS. Therefore, GFs with optimized structures and properties show great potentials in thermal management of form-factor-driven electronics and other high-power-driven systems.

Conductive Adhesive Based on Mussel-Inspired Graphene Decoration with Silver Nanoparticles.

Decoration with silver nanoparticles was obtained by coating graphene with a polydopamine layer, able to induce spontaneous metallic nanoparticles formation without any specific chemical interfacial modifier, neither using complex instrumentation. The choice of dopamine was inspired by the composition of adhesive proteins in mussels, related to their robust attach to solid surfaces. The synthesis procedure started from graphite and involved eco-friendly compounds, such as Vitamin C and glucose as reducing agent and water as reaction medium. Silver decorated graphene was inserted as secondary nanofiller in the formulation of a reference conductive adhesive based on epoxy resin and silver flakes. A wide characterization of the intermediate materials obtained along the step procedure for the adhesive preparation was carried out by several techniques. We have found that the presence of nanofiller yields, in addition to an improvement of the thermal conductivity (up to 7.6 W/m · K), a dramatic enhancement of the electrical conductivity of the adhesive. In particular, starting from 3 · 102 S/cm of the reference adhesive, we obtained a value of 4 · 104 S/cm at a nanofiller concentration of 11.5 wt%. The combined double filler conductivity was evaluated by Zallen's model. The effect of the temperature on the resistivity of the adhesive has been also studied.

Embedded Fin-Like Metal/CNT Hybrid Structures for Flexible and Transparent Conductors.

In this paper, an embedded fin-like metal-coated carbon nanotube (Fin-M/CNT) structure is demonstrated for flexible and transparent conductor wire applications. Embedded in a polydimethylsiloxane polymeric substrate, Fin-M/CNT wires with a minimum width of 5 µm and a minimum pitch of 10 µm have been achieved. Direct current resistances of single Fin-M/CNT wires, where the supporting CNT structures have been covered by Ti/Al/Au metal coatings of different thicknesses, have been measured. The high aspect ratio of the fin-like structures not only improves the adhesion between the wires and the polymeric substrate, but also yields a low resistance at a small surface footprint. In addition, transparent Fin-M/CNT grid lines with hexagonal patterns, with a sheet resistance of as low as 45 Ω sq(-1) , have been achieved at an optical transmittance of 88%. The robustness of the Fin-M/CNT structures has been demonstrated in bending tests up to 500 cycles and no significant changes in wire resistances are observed.

Vertically aligned CNT-Cu nano-composite material for stacked through-silicon-via interconnects.

For future miniaturization of electronic systems using 3D chip stacking, new fine-pitch materials for through-silicon-via (TSV) applications are likely required. In this paper, we propose a novel carbon nanotube (CNT)/copper nanocomposite material consisting of high aspect ratio, vertically aligned CNT bundles coated with copper. These bundles, consisting of hundreds of tiny CNTs, were uniformly coated by copper through electroplating, and aspect ratios as high as 300:1 were obtained. The resistivity of this nanomaterial was found to be as low as ∼10(-8) Ω m, which is of the same order of magnitude as the resistivity of copper, and its temperature coefficient was found to be only half of that of pure copper. The main advantage of the composite TSV nanomaterial is that its coefficient of thermal expansion (CTE) is similar to that of silicon, a key reliability factor. A finite element model was set up to demonstrate the reliability of this composite material and thermal cycle simulations predicted very promising results. In conclusion, this composite nanomaterial appears to be a very promising material for future 3D TSV applications offering both a low resistivity and a low CTE similar to that of silicon.

HB-EGF affects astrocyte morphology, proliferation, differentiation, and the expression of intermediate filament proteins.

Heparin-binding epidermal growth factor-like growth factor (HB-EGF), a vascular-derived trophic factor, belongs to the epidermal growth factor (EGF) family of neuroprotective, hypoxia-inducible proteins released by astrocytes in CNS injuries. It was suggested that HB-EGF can replace fetal calf serum (FCS) in astrocyte cultures. We previously demonstrated that in contrast to standard 2D cell culture systems, Bioactive3D culture system, when used with FCS, minimizes the baseline activation of astrocytes and preserves their complex morphology. Here, we show that HB-EGF induced EGF receptor (EGFR) activation by Y1068 phosphorylation, Mapk/Erk pathway activation, and led to an increase in cell proliferation, more prominent in Bioactive3D than in 2D cultures. HB-EGF changed morphology of 2D and Bioactive3D cultured astrocytes toward a radial glia-like phenotype and induced the expression of intermediate filament and progenitor cell marker protein nestin. Glial fibrillary acidic protein (GFAP) and vimentin protein expression was unaffected. RT-qPCR analysis demonstrated that HB-EGF affected the expression of Notch signaling pathway genes, implying a role for the Notch signaling in HB-EGF-mediated astrocyte response. HB-EGF can be used as a FCS replacement for astrocyte expansion and in vitro experimentation both in 2D and Bioactive3D culture systems; however, caution should be exercised since it appears to induce partial de-differentiation of astrocytes.

Stem cell responses to plasma surface modified electrospun polyurethane scaffolds.

The topographical effects from functional materials on stem cell behavior are currently of interest in tissue engineering and regenerative medicine. Here we investigate the influence of argon, oxygen, and hydrogen plasma surface modification of electrospun polyurethane fibers on human embryonic stem cell (hESC) and rat postnatal neural stem cell (NSC) responses. The plasma gases were found to induce three combinations of fiber surface functionalities and roughness textures. On randomly oriented fibers, plasma treatments lead to substantially increased hESC attachment and proliferation as compared to native fibers. Argon plasma was found to induce the most optimal combination of surface functionality and roughness for cell expansion. Contact guided migration of cells and alignment of cell processes were observed on aligned fibers. Neuronal differentiation around 5% was found for all samples and was not significantly affected by the induced variations of surface functional group distribution or individual fiber topography. FROM THE CLINICAL EDITOR: In this study the influence of argon, oxygen, and hydrogen plasma surface modification of electrospun polyurethane fibers on human embryonic stem cell and rat postnatal neural stem cell (NSC) responses is studied with the goal of clarifying the potential effects of functional materials on stem cell behavior, a topic of substantial interest in tissue engineering and regenerative medicine.

Bioactive 3D cell culture system minimizes cellular stress and maintains the in vivo-like morphological complexity of astroglial cells.

We tested the hypothesis that astrocytes grown in a suitable three-dimensional (3D) cell culture system exhibit morphological and biochemical features of in vivo astrocytes that are otherwise lost upon transfer from the in vivo to a two-dimensional (2D) culture environment. First, we report development of a novel bioactively coated nanofiber-based 3D culture system (Bioactive3D) that supports cultures of primary mouse astrocytes. Second, we show that Bioactive3D culture system maintains the in vivo-like morphological complexity of cultured cells, allows movement of astrocyte filopodia in a way that resembles the in vivo situation, and also minimizes the cellular stress, an inherent feature of standard 2D cell culture systems. Third, we demonstrate that the expression of gap junctions is reduced in astrocytes cultured in a 3D system that supports well-organized cell-cell communication, in contrast to the enforced planar tiling of cells in a standard 2D system. Finally, we show that astrocytes cultured in the Bioactive3D system do not show the undesired baseline activation but are fully responsive to activation-inducing stimuli. Thus, astrocytes cultured in the Bioactive3D appear to more closely resemble astrocytes in vivo and represent a superior in vitro system for assessing (patho)physiological and pharmacological responses of these cells and potentially also in co-cultures of astrocytes and other cell types.

A complete carbon-nanotube-based on-chip cooling solution with very high heat dissipation capacity.

Heat dissipation is one of the factors limiting the continuous miniaturization of electronics. In the study presented in this paper, we designed an ultra-thin heat sink using carbon nanotubes (CNTs) as micro cooling fins attached directly onto a chip. A metal-enhanced CNT transfer technique was utilized to improve the interface between the CNTs and the chip surface by minimizing the thermal contact resistance and promoting the mechanical strength of the microfins. In order to optimize the geometrical design of the CNT microfin structure, multi-scale modeling was performed. A molecular dynamics simulation (MDS) was carried out to investigate the interaction between water and CNTs at the nanoscale and a finite element method (FEM) modeling was executed to analyze the fluid field and temperature distribution at the macroscale. Experimental results show that water is much more efficient than air as a cooling medium due to its three orders-of-magnitude higher heat capacity. For a hotspot with a high power density of 5000 W cm(-2), the CNT microfins can cool down its temperature by more than 40 °C. The large heat dissipation capacity could make this cooling solution meet the thermal management requirement of the hottest electronic systems up to date.

Surface-confined synthesis of silver nanoparticle composite coating on electrospun polyimide nanofibers.

A methodology for fabricating hierarchical nanostructures by surface-confined synthesis of silver nanoparticles on electrospun polyimide nanofibers is reported. Through surface-confined imide cleavage at the dianhydride domain via immersion in an aqueous KOH solution, potassium polyamate coatings of accurately defined thickness are formed (at a rate of 25 nm h(-1) ). By utilizing the ion-exchange capability of the polyamate resin, silver ions are introduced through immersion in an aqueous AgNO3 solution. Subsequent reduction of the metal ion species leads to the formation of nanoparticles at the fiber surface. Two modes of reduction, chemical and thermal, are investigated in the report, each leading to distinct morphologies of the nanoparticle coatings. Via thermal reduction, a composite surface layer consisting of monodisperse silver nanoparticles (average diameter 5.2 nm) embedded in a re-imidized polyimide matrix is achieved. In the case of chemical reduction, the reduction process occurs preferentially at the surface of the fiber, leading to the formation of silver nanoparticles anchored at the surface, though not embedded, in a polyamic acid matrix. By regulating the modification depth, control of the particle density on the fiber surface is established. In both reduction approaches, the polyimide nanofiber core exhibits maintained integrity.

Graphene-Based Films: Fabrication, Interfacial Modification, and Applications.

Graphene-based film attracts tremendous interest in many potential applications due to its excellent thermal, electrical, and mechanical properties. This review focused on a critical analysis of fabrication, processing methodology, the interfacial modification approach, and the applications of this novel and new class material. Strong attention was paid to the preparation strategy and interfacial modification approach to improve its mechanical and thermal properties. The overview also discussed the challenges and opportunities regarding its industrial production and the current status of the commercialization. This review showed that blade coating technology is an effective method for industrial mass-produced graphene film with controllable thickness. The synergistic effect of different interface interactions can effectively improve the mechanical properties of graphene-based film. At present, the application of graphene-based film on mobile phones has become an interesting example of the use of graphene. Looking for more application cases is of great significance for the development of graphene-based technology.

A Novel Graphene Quantum Dot-Based mRNA Delivery Platform.

During the last decades, there has been growing interest in using therapeutic messager RNA (mRNA) together with drug delivery systems. Naked, unformulated mRNA is, however, unable to cross the cell membrane and is susceptible to degradation. Here we use graphene quantum dots (GQDs) functionalized with polyethyleneimine (PEI) as a novel mRNA delivery system. Our results show that these modified GQDs can be used to deliver intact and functional mRNA to Huh-7 hepatocarcinoma cells at low doses and, that the GQDs are not toxic, although cellular toxicity is a problem for these first-generation modified particles. Functionalized GQDs represent a potentially interesting delivery system that is easy to manufacture, stable and effective.

Degradation of Carbon Nanotube Array Thermal Interface Materials through Thermal Aging: Effects of Bonding, Array Height, and Catalyst Oxidation.

Carbon nanotube (CNT) array thermal interface materials (TIMs) are promising candidates for high-performance applications in terms of thermal performance. However, in order to be useful in commercial applications, the reliability of the interfaces is an equally important parameter, which so far has not been thoroughly investigated. In this study, the reliability of CNT array TIMs is investigated through accelerated aging. The roles of CNT array height and substrate configuration are studied for their relative impact on thermal resistance degradation. After aging, the CNT catalyst is analyzed using X-ray photoelectron spectroscopy to evaluate chemical changes. The CNT-catalyst bond appears to degrade during aging but not to the extent that the TIM performance is compromised. On the other hand, coefficient of thermal expansion mismatch between surfaces creates strain that needs to be absorbed, which requires CNT arrays with sufficient height. Transfer and bonding of both CNT roots and tips also create more reliable interfaces. Crucially, we find that the CNT array height of most previously reported CNT array TIMs is not enough to prevent significant reliability problems.

Aerosol Jet Printing of Graphene and Carbon Nanotube Patterns on Realistically Rugged Substrates.

Direct-write additive manufacturing of graphene and carbon nanotube (CNT) patterns by aerosol jet printing (AJP) is promising for the creation of thermal and electrical interconnects in (opto)electronics. In realistic application scenarios, this however often requires deposition of graphene and CNT patterns on rugged substrates such as, for example, roughly machined and surface-oxidized metal block heat sinks. Most AJP of graphene/CNT patterns has thus far however concentrated on flat wafer- or foil-type substrates. Here, we demonstrate AJP of graphene and single walled CNT (SWCNT) patterns on realistically rugged plasma-electrolytic-oxidized (PEO) Al blocks, which are promising heat sink materials. We show that AJP on the rugged substrates offers line resolution of down to ∼40 µm width for single AJP passes, however, at the cost of noncomplete substrate coverage including noncovered µm-sized pores in the PEO Al blocks. With multiple AJP passes, full coverage including coverage of the pores is, however, readily achieved. Comparing archetypical aqueous and organic graphene and SWCNT inks, we show that the choice of the ink system drastically influences the nanocarbon AJP parameter window, deposit microstructure including crystalline quality, compactness of deposit, and inter/intrapass layer adhesion for multiple passes. Simple electrical characterization indicates aqueous graphene inks as the most promising choice for AJP-deposited electrical interconnect applications. Our parameter space screening thereby forms a framework for rational process development for graphene and SWCNT AJP on application-relevant, rugged substrates.

Direct photolithographic patterning of electrospun films for defined nanofibrillar microarchitectures.

In this letter, a method of generating spatially defined electrospun microarchitectures by direct photolithographic patterning of electrospun films is described. A photoinitiator, benzoin methyl ether, is incorporated into a solid thermoplastic electrospun polyurethane matrix selectively photo-cross-linked by standard photolithographic methods. Subsequent development in an organic solvent yields spatially defined electrospun microstructures on a single substrate. Utilizing a multilayer approach, the method allows for the assembly of complex hierarchical electrospun structures on single substrates using methods analogous to the conventional microfabrication of solid-state devices.

Highly Oriented Graphite Aerogel Fabricated by Confined Liquid-Phase Expansion for Anisotropically Thermally Conductive Epoxy Composites.

Graphene-based thermally conductive polymer composites are of great importance for the removal of the excess heat generated by electronic devices. However, due to the orientation of graphene sheets in the polymer matrix, the through-plane thermal conductivity of polymer/graphene composites remains far from satisfactory. We here demonstrate a confined liquid-phase expansion strategy to fabricate highly oriented confined expanded graphite (CEG) aerogels. After being incorporated into epoxy resin (EP), the resulting EP/CEG composites exhibit a high through-plane thermal conductivity (4.14 ± 0.21 W m-1 K-1) at a quite low filler loading of 1.75 wt % (0.91 vol %), nearly 10 times higher than that of neat EP resin and 7.5 times higher than the in-plane thermal conductivity of the composite, indicating that the CEG aerogel has a high through-plane thermal conductivity enhancement efficiency that outperforms those of many graphite/graphene-based fillers. The facile preparation method holds great industrial application potential in fabricating anisotropic thermally conductive polymer composites.