Carbon dioxide is often promoted as a sustainable solvent, as CO 2 is non-flammable, exhibits a relatively low toxicity and is naturally abundant. However, injudicious use of carbon dioxide in a process or product can reduce rather than enhance overall sustainability. This review specifically examines the use of CO 2 to create greener processes and products, with a focus on research and commercialization efforts performed since 1995. The literature reveals that use of CO 2 has permeated almost all facets of the chemical industry and that careful application of CO 2 technology can result in products (and processes) that are cleaner, less expensive and of higher quality.

Supercritical and near-critical CO2 in green chemical synthesis and processing

The use of supercritical carbon dioxide as a processing solvent for the physical processing of polymeric materials is reviewed. Fundamental properties of CO2/polymer systems are discussed with an emphasis on available data and measurement techniques, the development of theory or models for a particular property, and an evaluation of the current state of understanding for that property. Applications such as impregnation, particle formation, foaming, blending, and injection molding are described in detail including practical operating information for selected topics. The review concludes with some forward-looking discussion on the future of CO2 in polymer processing.

A Review of CO2 Applications in the Processing of Polymers

https://pure.rug.nl/ws/files/6693298/2006ProgPolymSciNalawade.pdf

Supercritical carbon dioxide as a green solvent for processing polymer melts: Processing aspects and applications

Gas-expanded liquids.

https://hal-mines-albi.archives-ouvertes.fr/hal-01152908/document

New challenges in polymer foaming: A review of extrusion processes assisted by supercritical carbon dioxide

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

A high-pressure extrusion slit die rheometer was constructed to measure the viscosity of polymer melts plasticized by liquid and supercritical CO2. A novel gas injection system was devised to accurately meter the follow of CO2 into the extruder barrel. Measurements of pressure drop, within the die, confirm the presence of a one-phase mixture and a fully developed flow during viscosity measurements. Experimental measurements of viscosity as a function of shear rate, pressure, temperature, and CO2 concentration were conducted for three commercial polystyrene melts. The CO2 was shown to be an effective plasticizer for polystyrene, lowering the viscosity of the polymer melt by as much as 80%, depending of the process conditions and CO2 concentration. Existing theories for viscoelastic scaling of polymer melts and the prediction of Tg depression by a diluent were used to develop a free volume model for predicting the effects of CO2 concentration and pressure on polymer melt rheology. The free volume model, dependent only on material parameters of the polymer melt and pure CO2, was shown to accurately collapse the experimental data onto a single master curve independent of pressure and CO2 concentration for each of the three polystyrene samples. This model constitutes a simple predictive set of equations to quantify the effects of gas-induced plasticization on molten polymer systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3168–3180, 2000

High-pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships

A new experimental device is used to monitor in situ the swelling behavior of poly(dimethylsiloxane) melts in contact with supercritical carbon dioxide. The effects of pressure, temperature, and sample molecular weight on the kinetics and extent of swelling are examined using this experimental technique. The swelling kinetics of all polymer samples exhibit two distinct regimes:  an initial region of large swelling in which the diffusion of CO2 into the polymer follow Fickian behavior and a subsequent region of small volume increase asymptotic to an equilibrium swelling value. Diffusion coefficients of CO2, obtained from the initial swelling kinetics data, are found to be relatively insensitive to pressure, increase with temperature, and decrease with polymer molecular weight with the latter exhibiting a power-law dependence with an exponent of ∼−2. The extent of swelling increases with both pressure and molecular weight but exhibits different trends with temperature depending on system pressure. For press...

Carbon Dioxide-Induced Swelling of Poly(dimethylsiloxane)

High-pressure rheological behavior of polymer melts containing dissolved carbon dioxide (CO 2 ) at concentrations up to 6 wt % were investigated using a high-pressure extrusion slit die rheometer. In particular, the steady shear viscosity of poly(methyl methacrylate), polypropylene, low-density polyethylene, and poly(vinylidene fluoride) with dissolved CO 2 were measured for shear rates ranging from 1 to 500 s -1 and under pressure conditions up to 30 MPa. The viscosity of all samples revealed a reduction in the presence of CO 2 with its extent dependent on CO 2 concentration, pressure, and the polymer used. Two types of viscoelastic scaling models were developed to predict the effects of both CO 2 concentration and pressure on the viscosity of the polymer melts. The first approach utilized a set of equations analogous to the Williams-Landel-Ferry equation for melts between the glass-transition temperature (T g ) and T g + 100 °C, whereas the second approach used equations of the Arrhenius form for melts more than 100 °C above T g . The combination of these traditional viscoelastic scaling models with predictions for T g depression by a diluent (Chow model) were used to estimate the observed effects of dissolved CO 2 on polymer melt rheology. In this approach, the only parameters involved are physical properties of the pure polymer melt that are either available in the existing literature or can be measured under atmospheric conditions in the absence of CO 2 . The ability of the proposed scaling models to accurately predict the viscosity of polymer melts with dissolved high-pressure CO 2 were examined for each of the polymer systems.

High-pressure rheology and viscoelastic scaling predictions of polymer melts containing liquid and supercritical carbon dioxide

Polymeric materials having a plurality of cells formed therein are described. The polymeric materials include a foamed layer comprising a plurality of uniform microcells, nanocells or combinations thereof in a closed cell network, a transition layer positioned adjacent to the foamed layer, and at least one unfoamed outer layer positioned adjacent to the transition layer. The foamed layer may be present in a volume ranging from about 80 to about 99 percent based on the volume of the polymeric material, the transition layer may present in a volume ranging from about 0 to about 10 percent based on the volume of the polymeric material, and the at least one outer layer may be present in a volume ranging from about 0.01 to about 10 percent based on the volume of the polymeric material. Methods of making such polymeric materials are also described, as are apparatus for providing foamed polymeric materials.

Joseph R. Royer

Papers

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

High-pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships

Carbon Dioxide-Induced Swelling of Poly(dimethylsiloxane)

High-pressure rheology and viscoelastic scaling predictions of polymer melts containing liquid and supercritical carbon dioxide

Nano- and micro-cellular foamed thin-walled material, and processes and apparatuses for making the same