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Publication Title | Recent Developments in Materials Synthesis and Processing Using Supercritical CO2

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Recent Developments in Materials Synthesis and Processing Using Supercritical CO2**

By Andrew I. Cooper*

The chemical and physical properties of carbon dioxide in the liquid or supercriti-

cal state differ quite strongly from those of conventional liquid organic solvents.

These differences may be exploited in a wide variety of materials applications.

Here we describe recent research involving the use of dense carbon dioxide in the areas of porous organic materials, coatings and lithography, metal nanoparticle synthesis, and biomaterials processing.

1. Introduction

Supercritical carbon dioxide (scCO2) has attracted much interest recently as an alternative solvent for materials synthesis and processing.[1] Researchers have promoted CO2 as a sustain- able and agreeno solvent because it is non-toxic, non-flam- mable, and naturally abundant. In fact, the economics of using dense CO2 on an industrial scale are usually complex and must be assessed on a case-by-case basis.[2] Issues such as capital costs associated with high-pressure equipment and the energy re- quirements for compressing CO2 into the dense state may prove prohibitive in many instances. Nevertheless, it is widely accepted that the advantages associated with this solvent are likely to lead to a number of new CO2-based processes. The level of interest in supercritical fluid (SCF) technology can be gauged from the growing number of participating academic and industrial re- search groups world-wide. We highlight here four research areas of special interest in the field of advanced materials. We de- scribe how the unusual physical properties of CO2 (i.e., low tox- icity, easy separations, variable density, low viscosity, low surface tension, and polymer plasticization) are exploited in each case.

2. Results and Discussion

2.1. Porous Organic Materials

±Carbon dioxide has been studied extensively as an alter- native solvent for polymer synthesis.[3] Several groups have investigated the production of porous polymeric materials

[*] Dr. A. I. Cooper

Donnan and Robert Robinson Laboratories Department of Chemistry

University of Liverpool

Crown Street, Liverpool, L69 3BX (UK) E-mail: aicooper@liv.ac.uk

[**] Dr. Cooper is grateful to the Royal Society for provision of a Royal So- ciety University Research Fellowship.

using scCO2 as a solvent and/or foaming agent. Beckman and Hamilton have developed a one-step process that uses scCO2 to produce low-density microcellular fluorinated ma- terials.[4] Fluorinated compounds (Fig. 1a) were designed and synthesized, which dissolve in scCO2 and then associate to form gels. Upon removal of the CO2 phase, the gels pro-

Fig. 1. a) A CO2-soluble trifunctional urea. b) Scanning electron microscopy (SEM) image of a free-standing foam produced from this urea by gelation of a 5 wt.-% solution in scCO2 (scale bar = 20 lm). Bulk density of the foam is approximately 0.09 g/cm3.

Adv. Mater. 2001, 13, No. 14, July 18 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001 0935-9648/01/1407-1111 $ 17.50+.50/0 1111

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