The focus of this work is to examine the effect of flow rate ratio (quotient of the dispersed phase flow rate over the continuous phase flow rate) on a regime transition from squeezing to dripping at constant capillary numbers. The effect of the flow rate ratio on the volume of droplets generated in a microfluidic T-junction is discussed, and a new scaling law to estimate their volume is proposed. Existing work on a regime transition reported by several researchers focuses on the effect of the capillary number on regime transition, and the results that are presented in this paper advance the current understanding by indicating that the flow rate ratio is another parameter that dictates regime transition. In this paper, the transition between squeezing and dripping regimes is reported at constant capillary numbers, with a transition region identified between squeezing and dripping regimes. Dripping is observed at lower flow rate ratios and squeezing at higher flow rate ratios, with a transition region between the two regimes at flow rate ratios between 1 and 2. This is presented in a flow regime map that is constructed based on the observed mechanism. A scaling model is proposed to characterise droplet volume in terms of flow rate ratio and capillary number. The effect of flow rate ratio on the non-dimensional droplet volume is presented, and lastly, the droplet volume is expressed in terms of a range of parameters, such as the viscosity ratio between the dispersed and the continuous phase, capillary number, and the geometrical characteristics of the channels.

A millifluidic reactor was utilized for the synthesis of monodisperse, high magnetic moment, iron carbide (FexCy) nanoparticles by thermal decomposition of iron pentacarbonyl (Fe(CO)5). The effect of reaction conditions (temperature and pressure) on the size, morphology, crystal structure and magnetic properties of the nanoparticles was investigated. The system developed facilitated the thermal decomposition of precursor at reaction conditions (up to 265 °C and 4 bar) that cannot be easily achieved in conventional batch reactors. The degree of carbidization was enhanced by operating at elevated tempera-ture and pressure. The nanoparticles synthesized in the flow reactor had size 9-18 nm and demonstrated high saturation magnetisation (up to 164 emu/gFe). They further showed good stability against oxidation after two months of exposure in air, retaining good saturation magnetization values with a change of no more than 10% of the initial value. The heating ability of the nanoparticles in alternating magnetic field was comparable with other ferrites reported in literature, having intrinsic loss power values up to 1.52 (nHm2 kg-1).

Gas–liquid reactions are poorly explored in the context of nanomaterials synthesis, despite evidence of significant effects of dissolved gas on nanoparticle properties. This applies to the aqueous synthesis of iron oxide nanoparticles, where gaseous reactants can influence reaction rate, particle size and crystal structure. Conventional batch reactors offer poor control of gas–liquid mass transfer due to lack of control on the gas–liquid interface and are often unsafe when used at high pressure. This work describes the design of a modular flow platform for the water-based synthesis of iron oxide nanoparticles through the oxidative hydrolysis of Fe²⁺ salts, targeting magnetic hyperthermia applications. Four different reactor systems were designed through the assembly of two modular units, allowing control over the type of gas dissolved in the solution, as well as the flow pattern within the reactor (single-phase and liquid–liquid two-phase flow). The two modular units consisted of a coiled millireactor and a tube-in-tube gas–liquid contactor. The straightforward pressurization of the system allows control over the concentration of gas dissolved in the reactive solution and the ability to operate the reactor at a temperature above the solvent boiling point. The variables controlled in the flow system (temperature, flow pattern and dissolved gaseous reactants) allowed full conversion of the iron precursor to magnetite/maghemite nanocrystals in just 3 min, as compared to several hours normally employed in batch. The single-phase configuration of the flow platform allowed the synthesis of particles with sizes between 26.5 nm (in the presence of carbon monoxide) and 34 nm. On the other hand, the liquid–liquid two-phase flow reactor showed possible evidence of interfacial absorption, leading to particles with different morphology compared to their batch counterpart. When exposed to an alternating magnetic field, the particles produced by the four flow systems showed ILP (intrinsic loss parameter) values between 1.2 and 2.7 nHm²/kg. Scale up by a factor of 5 of one of the configurations was also demonstrated. The scaled-up system led to the synthesis of nanoparticles of equivalent quality to those produced with the small-scale reactor system. The equivalence between the two systems is supported by a simple analysis of the transport phenomena in the small and large-scale setups.