Anomalous freezing and melting behaviour of capillary confined CO2

In this paper we present our recent positron annihilation study of the liquid»solid phase boundary for CO₂ confined in nanometer pores of VYCOR glass. We find that CO₂ remains liquid in the pores far below the bulk freezing temperature and there is pronounced hysteresis between freezing and melting compared to that seen at the gas-liquid boundary in the pores. On freezing we see evidence of open space created in the pores. This leads to complex melting behaviour possibly involving the formation of gas-liquid interfaces. We see that frezing in the pores is totally irreversible, so that any solid which forms (no matter how small) remains stable up to the higher melting temperature. In contrast melting is more reversible (possibly indicating nucleation centres which permit immediate re-freezing). Finally, the pre-frozen state in the pores is different to the post-melted state.     

Diamond and diamond-like carbon from a preceramic polymer

The synthesis of poly(hydridocarbyne), one of a class of carbon-based random network polymers and a structural isomer of polyacetlyene, is reported. The network backbone of this polymer is primarily composed of tetrahedrally hybridized carbon atoms, each bearing one hydride substituent and linked via three carbon-carbon single bonds into a three-dimensional random network of fused rings. This atomic-level carbon network backbone confers unusual properties on the polymer, including facile thermal decomposition to form diamond or diamond-like carbon high-quality films at atmospheric pressure, by direct deposition or by chemical vapor deposition (CVD), without the use of hydrogen or any other reagent.     

Structural Consequences of S → Se Substitution in some Symmetrical [M(S2CNR2)3] Complexes

The consequences of replacement of the symmetrically chelate ligands in [M(E₂CNR₂)₃] (E = S, Se) complexes of potential 32 symmetry by analogous mixed S,Se unsymmetrical chelates are explored for both small (M = Co) and large (M = In) metal atoms, and R = primary (Et) and secondary (ⁱPr) alkyl substituents by way of low‐temperature single crystal X‐ray studies of [(Co(SSeCNEt₂)₃] ([Co(Se₂CNEt₂)₃] also determined as datum), and [In(SSeCNR₂)₃], R = Et, ⁱPr. The structure of [(ⁱPr₂N·CS·Se)₂] is also recorded.     

Phase behaviour near the triple point of carbon dioxide confined in mesoporous VYCOR glass

The phase behaviour of carbon dioxide confined in VYCOR glass at pressures below that of the bulk triple point (0.51 MPa) has been investigated. The temperature at which freezing occurs appears to be pressure dependent below 0.3 MPa. As experiments are performed at successively lower pressures, the confined phase transitions gradually disappear, due to either partial pore filling, or the proximity of the confined triple point.     

Positron and positronium annihilation studies of phase behaviour in confined geometry

In this paper we present a brief review of the current state of positron annihilation research into the phase behaviour of fluids confined within restricted boundaries. We summarise, in the form of selected examples, the work done so far on: (1) fluids confined in the nanometer-size pores of VYCOR glass, with particular emphasis on the confined phase diagram and the mechanisms behind phase transitions compared to bulk. (2) The adsorption/physisorption of gases on internal surfaces of grafoil and the potential of positron technique for revealing physical properties, such as the intricate molecular arrangements during phase transitions of the layered fluid.