Influence of the ultrasound cavitation intensity on reduced graphene oxide functionalization

Graphene is a valuable and useful nanomaterial due to its exceptionally high tensile strength, electrical conductivity and transparency, as well as the ability to tune its materials properties via functionalization. One of the most important features needed to integrate functionalized graphene into products via scalable processing is the effectiveness of graphene dispersion in aqueous and organic solvents. In this study, we aimed to achieve the functionalization of reduced graphene oxide (rGO) by sonication in a one-step process using polyvinyl alcohol (PVA) as a model molecule to be bound to the rGO surface. We investigated the influence of the sonication energy on the efficacy of rGO functionalization. The correlation between the performance of the high-intensity ultrasonic horn and the synthesis of the PVA functionalized rGO was thoroughly investigated by TGA coupled with MS, and IR, Raman, XPS, Laser diffraction, and SEM analysis. The results show that the most soluble PVA-functionalized rGO is achieved at 50% of the ultrasonic horn amplitude. Analysis of cavitation dynamics revealed that in the near vicinity of the horn it is most aggressive at the highest amplitude (60%). This causes rGO flakes to break into smaller domains, which negatively affects the functionalization process. On the other hand, the maximum of the pressure pulsations far away from the horn is reached at 40% amplitude, as the pressure oscillations are attenuated significantly in the 2-phase flow region at higher amplitudes. These observations corelate well with the measured degree of functionalization, where the optimum functionalized rGO dispersion is reached at 50% horn amplitude, and generally imply that cavitation intensity must be carefully adjusted to achieve optimal rGO functionalization.     

Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes

Treatment of crystalline graphite fine powder with an aqueous solution of the harmless and versatile substance polyvinylpyrrolidone under sonication results in water-soluble, polymer-protected graphene single layers without oxidation or destruction of the sp² character of the carbon core. The liquid-phase extraction of graphene monolayers was evidenced by TEM and AFM techniques, while their graphitic character was checked with Raman spectroscopy. Besides PVP, the water-soluble biopolymers albumin and sodic carboxymethylcellulose were also employed successfully in the aqueous-phase exfoliation of graphite, thereby supporting the generic character of the present method using a variety of suitable polymeric extractants.     

Fabrication of ultrasound-mediated tunable graphene oxide nanoscrolls

In this work, a cost-effective and facile method was adopted for the fabrication of graphene oxide nanoscrolls (GONS) by low frequency (20 kHz) ultrasonication with tunable dimensions. The graphene oxide (GO) was synthesized by modified Hummer’s method using synthetic graphite as a base material. Later, GO suspension (0.05 g L⁻¹) were made using methanol as solvent and subjected to different ultrasonication conditions. It was found that GO sheets curls themselves into nanoscrolls by overcoming the energy barrier for scrolling with the help of bubble cavitation energy provided by ultrasonication. Also, the effect of ultrasonication power (100–150 W) for irradiation time (0.5–3 h) over the GONS dimensions were investigated. The spiral wounded GONS structures were shown using electron microscopy. Raman Spectroscopy, Thin-film X-Ray Diffraction, Energy Dispersive X-Ray, FT Infrared Spectroscopic analysis were also done to endorse GONS formation. Factors affecting GONS formation such as sonication power and solvent selection were studied as scrolling of GO sheets are strongly dependent on sonication parameters and solvent characteristics. It was found that GONS length varies inversely with irradiation time for identical power density. Also, a solvent with relatively large Hansen solubility parameter, lower dipole movement and less negative value of zeta potential support GONS formation of longer length. Raman analysis overlays the rapid oxygen-defect site cleavage mechanism. The obtained GONS unlocks further developments in various engineering applications like adsorption, drug delivery and filtration membrane.     

Raman spectroscopy of graphene and carbon nanotubes

This paper reviews progress that has been made in the use of Raman spectroscopy to study graphene and carbon nanotubes. These are two nanostructured forms of sp² carbon materials that are of major current interest. These nanostructured materials have attracted particular attention because of their simplicity, small physical size and the exciting new science they have introduced. This review focuses on each of these materials systems individually and comparatively as prototype examples of nanostructured materials. In particular, this paper discusses the power of Raman spectroscopy as a probe and a characterization tool for sp² carbon materials, with particular emphasis given to the field of photophysics. Some coverage is also given to the close relatives of these sp² carbon materials, namely graphite, a three-dimensional (3D) material based on the AB stacking of individual graphene layers, and carbon nanoribbons, which are one-dimensional (1D) planar structures, where the width of the ribbon is on the nanometer length scale. Carbon nanoribbons differ from carbon nanotubes is that nanoribbons have edges, whereas nanotubes have terminations only at their two ends.     

Investigation of Raman and photoluminescence studies of reduced graphene oxide sheets

In this paper, we are investigating the Raman and photoluminescence properties of reduced graphene oxide sheets (rGO). Moreover, graphene oxide (GO) sheets are synthesized using Hummer’s method and further reduced into graphene sheets using D-galactose. Both GO and rGO are characterized by UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Thermogravimetric (TGA) analysis. Raman analysis of rGO shows the restoration of graphitic domains in GO after reduction. The photoluminescence of rGO showed emission in the UV region which is blue shifted along with luminescent quenching as compared to GO. This blue shift and quenching in photoluminescence arises due to the newly formed crystalline sp² clusters in rGO which created percolation pathways between the sp² clusters already present.     

Dispersion of nanoparticles: From organic solvents to polymer solutions

This work is devoted to a systematic study of nanoparticle dispersion by ultrasonication in different solutions: from organic solvents to polymer solutions. The cluster size of nanoparticles at different concentrations in both organic solvents and polymer solutions were directly characterized by Dynamic Light Scattering to study the effect of solid concentration, surfactant and polymer on the dispersion. It reveals that in stabilized suspensions, the smallest attainable size or aggregate size of nanoparticles is independent of solvent type and solid content over the tested range. Furthermore, nanoparticles in simple solvent and in polymer solutions had the similar evolution of cluster size and almost the same final size, which could be very helpful to optimize the dispersion of nanofillers in polymer solutions and nanocomposites. It is also shown that, with appropriate sonication amplitudes, the dispersion procedure developed for very dilute suspensions could be transferred to higher concentration suspensions or even to polymer suspensions.     

One-step preparation of hierarchical superparamagnetic iron oxide/graphene composites via hydrothermal method

In this paper, graphene/magnetite composites with hierarchical Fe₃O₄ structures were synthesized via a one-step hydrothermal method. The size of Fe₃O₄ nanocrystals and nanocrystal clusters can easily be controlled by altering reaction time and the starting mixed solvent ratio, respectively. Raman measurements evidenced that graphene oxide was simultaneously reduced to graphene during the deposition of magnetite particles. The deposition of Fe₃O₄ nanocrystals and nanocrystal clusters impedes graphene to restore the graphite structure. The composites showed a high crystallinity of magnetite and a considerable saturation magnetization. Furthermore, the acrylate modified Fe₃O₄ makes the composites water-dispersible and can effectively load polyfluorene polyelectrolyte via electrostatic force. The high magnetism, excellent water dispersibility and strong photoluminescence make these composites ideal candidates for various important applications such as magnetic resonance imaging, bioseparation, bioimaging, and optical devices fabrication.     

Raman spectroscopy of a-C:H:N films deposited using ECR-CVD with mixed gas

Ultraviolet (UV) and visible Raman spectroscopy were used to study a-C:H:N films deposited using ECR-CVD with a mixed gas of CH₄ and N₂. Small percentage of nitrogen from 0 to 15% is selected. Raman spectra show that CN bonds can be directly observed at 2220 cm⁻¹ from the spectra of visible and UV Raman. UV Raman enhances the sp¹ CN peak than visible Raman. In addition, the UV Raman spectra can reveal the presence of the sp³ sites. For a direct correlation of the Raman parameter with the N content, we introduced the G peak dispersion by combining the visible and UV Raman. The G peak dispersion is directly relative to the disorder of the sp² sites. It shows the a-C:H:N films with higher N content will induce more ordered sp² sites. In addition, upper shift of T position at 244 nm excitation with the high N content shows the increment of sp² fraction of films. That means the films with high N content will become soft and contain less internal stress. Hardness test of films also confirmed that more N content is with less hardness.     

Graphene Modified Lipophilically by Stearic Acid and its Composite With Low Density Polyethylene

Graphene, prepared by the thermal reduction of graphite oxide (GO), was modified with stearic acid to enhance its lipophilicity. A novel method, using the intrinsic epoxy groups on the graphene, was utilized for reaction with stearic acid to minimize the negative impact of the normal functionalization method on the π-electronic system of graphene. Gravimetric analysis, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) showed that the stearic acid was effectively attached to the graphene. In addition, Raman spectroscopy and electric conductivity of the graphene showed that this novel modification method, utilizing intrinsic defects, did not damage the π-electronic system of the sp² bonded carbons. The dispersion of graphene in a low density polyethylene (LDPE) matrix was enhanced; consequently, the reinforcing effect in tensile testing was improved by the lipophilic modification. The crystallization behavior observed by differential scanning calorimetry (DSC) showed that the crystallization of LDPE was hindered by dispersed graphene, more evidently when dispersed uniformly.     

Effect of sinusoidal ripples in refractive index profile distribution on the performance characteristics of dual concentric core step index fiber Raman amplifier

Phased matched wavelength, effective area, effective Raman gain, and wave guide dispersion are computed from exact numerical solution assuming scalar wave equation in the presence and absence of ripples as imperfections in the refractive index profile in dual cores of single mode fiber Raman amplifier for the first time. It is observed that for larger values of amplitude and lower frequencies, the effective Raman gain increases w.r.t. that calculated with no ripples. However, we assume ripple amplitude up to 5% of core cladding refractive index difference w.r.t. the available data, corresponding to the three ranges of relative ripple amplitudes of 1%, 2%, 3% and ripple frequencies of 1, 2, 3 μm⁻¹. Based on these data, we analyse performance of FRA over frequency shift band of 20–700 cm⁻¹. Uniformity of gain is interestingly seen to be maintained for higher ripple frequency and lower amplitude. However, no prominent effect in coefficient of dispersion and phase matched wavelength is observed within operating range of wavelength. Also, based on available structural parameter, the investigation should find use as a guide to system users to know the limit and promise of existence of ripples.     

Optical and structural properties of polycrystalline CVD diamond films grown on fused silica optical fibres pre-treated by high-power sonication seeding

In this paper, the growth of polycrystalline chemical vapour deposition (CVD) diamond thin films on fused silica optical fibres has been investigated. The research results show that the effective substrate seeding process can lower defect nucleation, and it simultaneously increases surface encapsulation. However, the growth process on glass requires high seeding density. The effects of suspension type and ultrasonic power were the specific objects of investigation. In order to increase the diamond density, glass substrates were seeded using a high-power sonication process. The highest applied power of sonotrode reached 72 W during the performed experiments. The two, most common diamond seeding suspensions were used, i.e. detonation nanodiamond dispersed in (a) dimethyl sulfoxide and (b) deionised water. The CVD diamond nucleation and growth processes were performed using microwave plasma assisted chemical vapour deposition system. Next, the seeding efficiency was determined and compared using the numerical analysis of scanning electron microscopy images. The molecular composition of nucleated diamond was examined with micro-Raman spectroscopy. The sp³/sp² band ratio was calculated using Raman spectra deconvolution method. Thickness, roughness, and optical properties of the nanodiamond films in UV–vis wavelength range were investigated by means of spectroscopic ellipsometry. It has been demonstrated that the high-power sonication process can improve the seeding efficiency on glass substrates. However, it can also cause significant erosion defects at the fibre surface. We believe that the proposed growth method can be effectively applied to manufacture the novel optical fibre sensors. Due to high chemical and mechanical resistance of CVD diamond films, deposition of such films on the sensors is highly desirable. This method enables omitting the deposition of an additional adhesion interlayer at the glass–nanocrystalline interface, and thus potentially increases transmittance of the optical system.     

Enhancement of lattice defect signatures in graphene and ultrathin graphite using tip‐enhanced Raman spectroscopy

Understanding the role of defects in graphene is the key to tailoring the properties of graphene and promoting the development of graphene‐based devices. Defects can affect the electronic properties of a device while also offering a means by which to functionalize the local properties. Using tip‐enhanced Raman spectroscopy (TERS), heightened defect sensitivity was demonstrated on graphene edges, folds, and overlapping regions. Measurements confirm that TERS can provide simultaneous structural and spectral information on a localized scale, hence offering defect characterization on a scale that is not obtainable using conventional Raman spectroscopy. This study observed preferential enhancement of the D band signal on multilayered graphene and ultrathin graphite; in addition, other key defect signatures were also enhanced and detected. We present our findings in relation to theoretical predictions of graphene defect signatures and an analysis of the sensitivity of TERS in measuring two‐dimensional structures. Copyright © 2013 John Wiley & Sons, Ltd.     

Ultrasound-promoted preparation of polyvinyl ferrocene-based electrodes for selective formate separation: Experimental design and optimization

The selective separation of ions is a major technological challenge having far-ranging impacts from product separation in electrochemical production of base chemicals from CO₂ to water purification. In recent years, ion-selective electrochemical systems leveraging redox-materials emerged as an attractive platform based on their reversibility and remarkable ion selectivity. In the present study, we present an ultrasound-intensified fabrication process for polyvinyl ferrocene (PVF)–functionalized electrodes in a carbon nanotube (CNT) matrix for selective electro-adsorption of formate ions. To this end, a response surface methodology involving the Box–Behnken design with three effective independent variables, namely, PVF to CNT ratio, sonication duration, and ultrasonic amplitude was applied to reach the maximum formate adsorption efficiency. The fabricated electrodes were characterized using cyclic voltammetry, X-ray diffraction, Raman spectroscopy, and scanning electron microscopy (SEM). SEM images revealed that an optimized ultrasonic amplitude and sonication time provided remarkable improvements in electrode morphology. Through a sedimentation study, we qualitatively demonstrate that the main optimized conditions improved PVF/CNT dispersion stability, consequently providing the highest number of active surface sites for adsorption and the highest adsorption efficiency. The highest percentage of active electrode surface sites and the maximum adsorption efficiency were 97.8 and 90.7% respectively at a PVF/CNT ratio of 3, ultrasonication time of one hour, and 50% ultrasonic amplitude.     

State of the art and recent advances in the ultrasound-assisted synthesis,exfoliation and functionalization of graphene derivatives

Sonochemistry, an almost a century old technique was predominantly employed in the cleaning and extraction processes but this tool has now slowly gained tremendous attention in the synthesis of nanoparticles (NPs) where particles of sub-micron have been produced with great stability. Following this, ultrasonication techniques have been largely employed in graphene synthesis and its dispersion in various solvents which would conventionally take days and offers poor yield. Ultrasonic irradiation allows the production of thin-layered graphene oxide (GO) and reduced graphene oxide (RGO) of up to 1 nm thickness and can be produced in single layers. With ultrasonic treatment, reactions were made easy whereby graphite can be directly exfoliated to graphene layers. Oxidation to GO can also be carried out within minutes and reduction to RGO is possible without the use of any reducing agents. In addition, various geometry of graphene can be produced such as scrolled graphene, sponge or foam graphene, smooth as well as those with rough edges, each serving its own unique purpose in various applications such as supercapacitor, catalysis, biomedical, etc. In ultrasonic-assisted reaction, deposition of metal NPs on graphene was more homogeneous with custom-made patterns such as core-shell formation, discs, clusters and specific deposition at the edges of graphene sheets. Graphene derivatives with the aid of ultrasonication are the perfect catalyst for various organic reactions as well as an excellent adsorbent. Reactions which used to take hours and days were significantly reduced to minutes with exceedingly high yields. In a more recent approach, sonophotocatalysis was employed for the combined effect of sonication and photocatalysis of metal deposited graphene. The system was highly efficient in organic dye adsorption. This review provides detailed fundamental concepts of ultrasonochemistry for the synthesis of graphene, its dispersion, exfoliation as well as its functionalization, with great emphasis only based on recent publications. Necessary parameters of sonication such as frequency, power input, sonication time, type of sonication as well as temperature and dual-frequency sonication are discussed in great length to provide an overview of the resultant graphene products.     

Triple‐resonant two‐phonon Raman scattering in graphene

The triple‐resonant (TR) second‐order Raman scattering mechanism in graphene is re‐examined. It is shown that the magnitude of the TR contribution to the photon‐G′ mode coupling function in graphene is one order of magnitude larger than the widely accepted two‐resonant coupling. Enhancement of the order of 100 in the Raman intensity, with respect to the usual double‐resonant model, is found for the G′ band in graphene, and is expected in the related sp²‐based carbon materials, as well. Copyright © 2011 John Wiley & Sons, Ltd.     

Graphene nanosheets: Ultrasound assisted synthesis and characterization

A facile sonochemical route for the synthesis of graphene nanosheets via reduction of graphene oxide (GO) has been reported. The synthesized graphene sheets are characterized using UV–vis spectra, Fourier transform infra-red (FT-IR) spectra, transmission electron microscope, X-ray photoelectron spectra (XPS) and Raman spectroscopic techniques. The UV–vis spectroscopy results showed that the absorption peak was red shifted due to the reduction of GO into graphene. FT-IR and XPS spectra revealed the removal of oxygenated functional groups in graphene after the reduction process. Raman spectra confirmed the restoration of new sp² carbon domains in graphene sheets after the reduction. The sonochemical approach for the synthesis of graphene nanosheets is relatively fast, cost-effective and efficient as compared to other methods.     

Orientation of sp2 carbon nanoclusters in ion‐implanted polymethylmethacrylate as revealed by polarized Raman spectroscopy

Raman spectroscopy is widely used for the characterization of bonding type in carbon‐based materials, including carbonized surface layer in ion‐implanted polymers. Studies of the polarization properties of Raman scattering from amorphous carbonaceous materials, however, are very scarce. In this paper, we investigate the polarized Raman spectra of polymethylmethacrylate (PMMA) implanted with 50‐keV Si⁺ ions at fluences in the range 3.2 × 10¹⁴–1.0 × 10¹⁷ ions/cm² and for different visible excitation wavelengths. The spectra of the implanted samples are dominated by the D‐ and G‐bands of sp² carbon, which evidence strong carbonization of the ion‐modified layer. The multiwavelength excitation allowed us to resonantly probe the depolarization ratios for sp² clusters of different sizes. We established that the depolarization ratio ρ_G of the G‐band correlates with the sp² cluster size approaching the random orientation limit of 0.75 for the smallest clusters and a limiting value of 0.41 for the largest clusters. The experimental findings give evidence for a preferable orientation of the larger size clusters with their hexagonal planes perpendicular to the surface of the sample. A plausible explanation for such an arrangement is that the sp² clusters form tile‐like arrangements along the ion tracks. This finding may give clues for understanding of the strong transconductance of the ion‐modified layer, and open prospects for the application of polarized Raman spectroscopy as a characterization tool for surface morphology in ion‐implanted materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.     

Sonication-assisted layer-by-layer deposition of gold nanoparticles for highly conductive gold patterns

Sonication-assisted layer-by-layer (LBL) deposition of gold nanoparticles (GNPs) was carried out in an attempt to prepare highly conductive gold patterns on polyimide substrates. First, sonication time was optimized with GNPs (12.8 nm) whose size was large enough to be analyzed by FE-SEM in order to evaluate the surface coverage. Next, multilayer formation (4, 8 and 12 layer) was confirmed using ethanedithiol (EDT) as linker molecules under optimized conditions by measuring their UV absorption, near-IR (NIR) transmittance, thickness, and electrical conductivity. Finally, 20-layer films using small GNPs (2.5 nm) were prepared with or without patterning, followed by sintering at 150 °C for 1 h, which provided clean gold patterns with high electrical conductivity (2.5 × 10⁵ Ω⁻¹ cm⁻¹).     

Anisotropic mechanical properties and Stone-Wales defects in graphene monolayer: A theoretical study

We investigate the mechanical properties of graphene monolayer via the density functional theoretical (DFT) method. We find that the strain energies are anisotropic for the graphene under large strain. We attribute the anisotropic feature to the anisotropic sp² hybridization in the hexagonal lattice. We further identify that the formation energies of Stone-Wales (SW) defects in the graphene monolayer are determined by the defect concentration and also the direction of applied tensile strain, correlating with the anisotropic feature.