TY - JOUR
T1 - Phase equilibriums, self-assembly and interactions in two-, three- and four medium-chain length component systems
AU - Rosenholm, Jarl B.
N1 - Funding Information:
The Academy of Finland is acknowledged for continuous support throughout this project and for funding the Center of Excellence for Functional Materials .
PY - 2014/3
Y1 - 2014/3
N2 - The Scandinavian surface (surfactant) and colloid science owes much of its success to Per Ekwall and Björn Lindman. In this review the main topics shared by their research groups at Åbo Akademi University in Finland and at Lund University in Sweden are described. The nature of surface active substances (cosolvents, co-surfactants and surfactants) and microemulsions are evaluated. It is shown that the properties of medium-chain length surfactants differ dramatically from long-chain surfactants. The phase equilibriums of binary systems are related to the phase equilibriums of ternary and quaternary systems referred to as microemulsions or more recently also as nanoemulsions. A distinction is made between hydrotrope liquids, detergentless microemulsions, surfactant mixture systems and microemulsions. Three component systems are assembled to "true" quaternary microemulsions. An exceptionally comprehensive network of thermodynamic parameters describing molecular site exchange and micelle formation are derived and related mutually. Gibbs free energy, enthalpy, entropy, volume, heat capacity, expansivity and compressibility can be used to illustrate the degree of aggregation cooperativity and to evaluate whether micelle formation is of a first-, second- or intermediate order phase transition. Theoretical simulations and experimental results show that the associate structures of medium-chain length surfactants are quite open and may be deformed due to small aggregation numbers. The self-assembly occurs over a number of distinct steps at a series of experimentally detectable critical concentrations. Despite the low aggregation tendency their phase behavior equals those of long-chain homologs in surfactant mixture and microemulsion systems. A number of models describing the self-assembly are reviewed. Nuclear magnetic resonance (shift, relaxation rate and diffusion), Laser Raman and infrared spectroscopies were chosen as key instruments for molecular interaction characterization since they were used in the collaboration between the research groups in Åbo and in Lund. A new method is introduced in order to evaluate the traditional procedure for extracting limiting parameters which also enables an illustration of the degree of cooperativity. The focus is laid mainly on aqueous, alcoholic, saline and, to a limited extent oil phases of one-, two-, three- and four component systems of water-sodium carboxylates-alcohol-oil. The extensive thermodynamic characterization of these liquid phases and liquid crystalline phases is left out due to space restrictions.
AB - The Scandinavian surface (surfactant) and colloid science owes much of its success to Per Ekwall and Björn Lindman. In this review the main topics shared by their research groups at Åbo Akademi University in Finland and at Lund University in Sweden are described. The nature of surface active substances (cosolvents, co-surfactants and surfactants) and microemulsions are evaluated. It is shown that the properties of medium-chain length surfactants differ dramatically from long-chain surfactants. The phase equilibriums of binary systems are related to the phase equilibriums of ternary and quaternary systems referred to as microemulsions or more recently also as nanoemulsions. A distinction is made between hydrotrope liquids, detergentless microemulsions, surfactant mixture systems and microemulsions. Three component systems are assembled to "true" quaternary microemulsions. An exceptionally comprehensive network of thermodynamic parameters describing molecular site exchange and micelle formation are derived and related mutually. Gibbs free energy, enthalpy, entropy, volume, heat capacity, expansivity and compressibility can be used to illustrate the degree of aggregation cooperativity and to evaluate whether micelle formation is of a first-, second- or intermediate order phase transition. Theoretical simulations and experimental results show that the associate structures of medium-chain length surfactants are quite open and may be deformed due to small aggregation numbers. The self-assembly occurs over a number of distinct steps at a series of experimentally detectable critical concentrations. Despite the low aggregation tendency their phase behavior equals those of long-chain homologs in surfactant mixture and microemulsion systems. A number of models describing the self-assembly are reviewed. Nuclear magnetic resonance (shift, relaxation rate and diffusion), Laser Raman and infrared spectroscopies were chosen as key instruments for molecular interaction characterization since they were used in the collaboration between the research groups in Åbo and in Lund. A new method is introduced in order to evaluate the traditional procedure for extracting limiting parameters which also enables an illustration of the degree of cooperativity. The focus is laid mainly on aqueous, alcoholic, saline and, to a limited extent oil phases of one-, two-, three- and four component systems of water-sodium carboxylates-alcohol-oil. The extensive thermodynamic characterization of these liquid phases and liquid crystalline phases is left out due to space restrictions.
KW - Cooperativity
KW - Hydrotrope-, surfactant mixture- and solvent systems
KW - New model for molecule interaction and self-assembled structure
KW - NMR-Laser-Raman-FTIR spectroscopy
KW - Order of phase transition
KW - Phase equilibriums
KW - Theoretical simulations
KW - Thermodynamic models for microemulsion formation
KW - Two-, three- and four component microemulsions
UR - http://www.scopus.com/inward/record.url?scp=84903367123&partnerID=8YFLogxK
U2 - 10.1016/j.cis.2013.08.009
DO - 10.1016/j.cis.2013.08.009
M3 - Review Article or Literature Review
AN - SCOPUS:84903367123
SN - 0001-8686
VL - 205
SP - 9
EP - 47
JO - Advances in Colloid and Interface Science
JF - Advances in Colloid and Interface Science
ER -