Dr Amanpreet Kaur

In this work, we implement a dual frequency (24 kHz and 1174 kHz) ultrasonic assisted liquid phase exfoliation (ULPE) technique in deionized water (DIW) and other eco-friendly solvents, to produce a variety of high-quality few-layer graphene (FLG) solutions under controlled ultrasonication conditions. The resulting FLG dispersions of variable sizes (∼0.2–1.5 μm2) confirmed by characterisation techniques comprising UV–Vis spectroscopy, Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM). For the first time we demonstrate that high yield of FLG flakes with minimal defects, stable for 6 + months in a solution (stability ∼ 70 %), can be obtained in less than 1-hour of treatment in either water/ethanol (DIW:EtOH) or water/isopropyl alcohol (DIW:IPA) eco-friendly mixtures.

We also scrutinized the underlying mechanisms of cavitation using high-speed imaging synchronized with acoustic pressure measurements. The addition of ethanol or IPA to deionized water is proposed to play a central role in exfoliation as it regulates the extend of the cavitation zone, the intensity of the ultrasonic field and, thus, the cavitation effectiveness. Our study revealed that lateral sizes of the obtained FLG depend on the choice of exfoliating media and the diameter of a sonotrode used. This variability offers flexibility in producing FLG of different sizes, applicable in a wide spectrum of size-specific applications.

Nowadays, one of the promising methods for scalable graphene production is ultrasound-aided liquid phase exfoliation (ULPE) of graphite. Two current limiting factors of ULPE are the use of harmful solutions (such as N-Methyl-2-pyrrolidone or Dimethylformamide) and a relatively low graphene yield. In this study, we demonstrate a new dual frequency (20 kHz and 1174 kHz) ULPE approach in various eco-friendly media, which enabled us to produce various few-layer graphene (FLG) solutions of high quality. By implementing sophisticated characterisation techniques consisting of Raman spectroscopy, UV–vis spectroscopy and high-resolution electron microscopy, the final graphene flakes structure was confirmed to correlate the properties of each individual solution. The thinner (∼3 layers) and larger (∼1.5 μm2) flakes were observed while using just water, with the highest yield (11%) of smaller FLG flakes to be achieved in the mixture of water and a surfactant. In order to understand the cavitation mechanism in different solutions, the ULPE process was investigated by acoustic measurements. This study demonstrates the crucial role of ethanol (as a solvent) and surfactants as it regulates the cavitation power and intensity of the ultrasonic field and, thereby, the cavitation effectiveness. It is suggested that the mixture of water, ethanol and a surfactant is the best medium for ULPE process where a high yield of low-defective FLG flakes can be obtained in a solution stable at least for 3 months (around 80%).

Ultrasonic cavitation is used in various processes and applications, utilizing powerful shock waves and high-speed liquid jets generated by the collapsing bubbles. Typically, a single frequency source is used to produce the desired effects. However, optimization of the efficiency of ultrasound reactors is necessary to improve cavitation activity in specific applications such as for the exfoliation of two dimensional materials. This research takes the next step to investigate the effect of a dual frequency transducer system on the bubble dynamics, cavitation zone, pressure fields, acoustic spectra, and induced shock waves for four liquids with a range of physical properties. Using ultra-high-speed imaging and synchronized acoustic pressure measurements, the effect of ultrasonic dual frequencies on bubble dynamics was investigated. The addition of a high frequency transducer (1174 kHz) showed that the bubble fragments and satellite bubbles induced from a low frequency transducer (24 kHz) were able to extend their lifecycle and increase spatial distribution, thus, extending the boundaries of the cavitation zone. Furthermore, this combination of ultrasonic frequencies generated higher acoustic pressures (up to 180%) and enhanced the characteristic shock wave peak, indicating more bubble collapses and the generation of additional shock waves. The dual frequency system also enlarged the cavitation cloud size under the sonotrode. These observations specifically delineated the enhancement of cavitation activity using a dual frequency system pivotal for optimization of existing cavitation-based processing technologies.

Ultrasonic assisted liquid phase exfoliation (ULPE) is a promising method for the large scale production of 2D materials. Currently, toxic solvents such as N-Methyl-2-pyrrolidone (NMP) are commonly used for the production of graphene. In this paper four solvents; three green solvents (water, ethanol and water/ethanol) plus NMP for comparison, were sonicated and examined in terms of their bubble dynamics and acoustic emissions. Advanced fundamental analysis was conducted using high-speed imaging synchronised with acoustic pressure measurements complemented by shadowgraphic photography of the emitted shockwaves, in order to determine a suitable eco-friendly solvent medium from a cavitation bubbles dynamics perspective. Thereafter, ULPE of graphite in the optimum solvent took place for 2 h under controlled ultrasonication parameters. The produced graphene samples were characterised by employing a series of techniques consisting of Ultraviolet–visible (UV–Vis) and Raman spectroscopy as well as transmission electron microscopy (TEM). A mixture of deionised water and ethanol was shown to produce a yield twice that of pure water, comprising of high quality few layer graphene (3–5 Ls) with an average area of ∼1.15 (μm)2 and stability of ∼78% for the duration of six months. This combination is a promising eco-friendly substitute for future commercial manufacturing of graphene.

Graphene dispersions in water are highly desirable for a range of applications such as biomedicines, separation membranes, coatings, inkjet printing and more. Recent novel research has been focussed on developing a green approach for scalable production of graphene. However, one important parameter, which is often neglected is the bulk temperature of the processing liquid. This paper follows our earlier work where optimal sono-exfoliation parameters of graphite in aqueous solutions were determined based on the measured acoustic pressure fields at various temperatures and input powers. Here, we take the next step forward and demonstrate using systematic characterisation techniques and acoustic pressure measurements that sonication-assisted liquid phase exfoliation (LPE) of graphite powder can indeed produce high quality few layer graphene flakes in pure water at a specific temperature, i.e. 40 °C, and at an optimised input generator power of 50%, within 2-h of processing. UV–vis analysis also revealed that the exfoliation, stability and uniformity of dispersions were improved with increasing temperature. We further confirmed the successful exfoliation of graphene sheets with minimal level of defects in the optimized sample with the help of Raman microscopy and transmission electron microscopy. This study demonstrated that understanding and controlling processing temperature is one of the key parameters for graphene exfoliation in water which offers a potential pathway for its large-scale production.