International audienceIt is well known that supercritical carbon dioxide (sc-CO 2) is soluble in molten polymers and acts as a plasticizer. The dissolution of sc-CO 2 leads to a decrease in the viscosity of the liquid polymer, the melting point and the glass transition temperature. These properties have been used in several particle generation processes such as PGSS (particles from gas saturated solutions). It is therefore highly likely that extrusion processes would benefit from the use of sc-CO 2 since the rationale of the extrusion processes is to formulate, texture and shape molten polymers by forcing them through a die. Combining these two technologies, extrusion and supercritical fluids, could open up new applications in extrusion. The main advantage of introducing sc-CO 2 in the barrel of an extruder is its function as a plasticizer, which allows the processing of molecules which would otherwise be too fragile to withstand the mechanical stresses and the operating temperatures of a standard extrusion process. In addition, the dissolved CO 2 acts as a foaming agent during expansion through the die. It is therefore possible to control pore generation and growth by controlling the operating conditions. This review focuses on experimental work carried out using continuous extrusion. A continuous process is more economically favourable than batch foaming processes because it is easier to control, has a higher throughput and is very versatile in the properties and shapes of the products obtained. The coupling of extrusion and supercritical CO 2 technologies has already broadened the range of application of extrusion processes. The first applications were developed for the agro-food industry twenty years ago. However, most thermoplastics could potentially be submitted to sc-CO 2-assisted extrusion, opening new challenging opportunities, particularly in the field of pharmaceutical applications. This coupled technology is however still very new and further developments of both experimental and modelling studies will be necessary to gain better theoretical understanding and technical expertise prior to industrial use, especially in the pharmaceutical field
In the pharmaceutical industry, an even greater number of products are in the form of particulate solids. Their formation, formulation and the control of their user properties are still not well understood and mastered. Since the mid-1980s, a new method of powder generation has appeared involving crystallisation with supercritical fluids. Carbon dioxide is the most widely used solvent and its innocuity and ''green'' characteristics make it the best candidate for the pharmaceutical industry. Rapid Expansion of Supercritical Solutions (RESS), Supercritical Anti Solvent (SAS) and Particles from Gas Saturated Solutions (PGSS) are three families of processes which lead to the production of fine and monodisperse powders, including the possibility of controlling crystal polymorphism. For the RESS process, the sudden decompression of the fluid in which a solute has been dissolved is the driving force of nucleation. CO 2 is, however, a rather feeble solvent and this is obviously the main limitation of the development of RESS. In the SAS process, CO 2 acts as a non-solvent for inducing the crystallisation of a solute from an organic solution. The versatility of SAS (there is always a proper solvent-antisolvent couple for the studied solute) ensures future developments for very different types of materials. PGSS uses the fact that it is much easier to dissolve CO 2 in organic solutions (or melted compounds) than the contrary. It presents very promising perspectives of industrial development. After almost 20 years of active research, and more than 10 years of process development, this technology is reaching maturity, and very soon commercial drug produced by these techniques are likely to appear.
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