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Catanionic Surfactant Mixtures and Binary Systems of Modified Fatty Acid Surfactants. Phase Equilibria and Structure.

Bydén Sjöbom, Malin LU (2002)
Abstract
Surfactant self-assembly is an important phenomenon that occurs in a number of processes in our everyday life. It is important to understand the forces and parameters that control and influence the self-assembly, as this knowledge can be used both in order to design surfactant systems with desired properties and for creating model systems, for example for biological processes. The papers of this thesis all concern the phase equilibria of ionic surfactant systems, which have been investigated by means of <sup>2</sup>H NMR, optical methods and SAXS.



The aqueous ternary phase diagrams of 1-dodecylpyridinium bromide, with dodecane and dodecanol as the respective third component, were studied.



... (More)
Surfactant self-assembly is an important phenomenon that occurs in a number of processes in our everyday life. It is important to understand the forces and parameters that control and influence the self-assembly, as this knowledge can be used both in order to design surfactant systems with desired properties and for creating model systems, for example for biological processes. The papers of this thesis all concern the phase equilibria of ionic surfactant systems, which have been investigated by means of <sup>2</sup>H NMR, optical methods and SAXS.



The aqueous ternary phase diagrams of 1-dodecylpyridinium bromide, with dodecane and dodecanol as the respective third component, were studied.



The sodium 2-methyldecanoate was proved to have a very low Krafft-temperature in the solution phase, about 1 °C. Both the pure (R)- and the racemic surfactant formed the same phase sequence with water as have been seen for sodium decanoate, although at lower temperatures. They also form a very narrow intermediate phase, with a so far unknown structure.



The phase equilibria of the binary aqueous systems of a-methylated sodium octanoate, -nonanoate and -dodecanoate respectively, were studied. The two former show a phase sequence very similar to sodium octanoate. The latter has a phase sequence different from its unsubstituted analog, as we have not been able to isolate any hexagonal structure, and only one intermediate phase, most likely a rhombhohedrical structure.



In the pseudo-ternary DoTAC-sodium carboxylate-water systems, the level of asymmetry was proven to play an important role for the extension of both micellar solutions and liquid crystalline phases. The combination DoTAC-sodium octanoate seemed to be the most suitable for the formation of a mixed hexagonal structure, whereas sodium decanoate gave the largest lamellar phase. All three systems form mixed micelles at carboxylate/DoTAC molar ratios <1, and coexisting aggregates or aggregates and monomers at higher ratios. Within the DoTAC-decanoate solution phase, there is a narrow coacervation area around equimolarity.



The complete pseudo-ternary phase diagram of the DDAB-sodium taurodeoxycholate-water system was presented. The DDAB-rich side was studied by means of <sup>2</sup>H NMR and SAXS, whereas NMR self-diffusion measurements were performed in the large solution phase. The latter results indicate that the solution phase is consistent of aggregates with positive curvature throughout its whole range of existence. (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Professor Rosenholm, Jarl. B., Åbo Academy University, Finland
organization
publishing date
type
Thesis
publication status
published
subject
keywords
coacervation, asymmetry, bile salt, didodecyldimethylammonium bromide, Physical chemistry, Fysikalisk kemi, catanionic surfactant mixture, intermediate phase, a-methylsubstituted sodium carboxylate, dodecylpyridinium bromide, ionic surfactant, polarizing microscopy, FT-PGSE self-diffusion, 2H NMR, SAXS, liquid crystal, micelle, phase equilibria, phase diagram
pages
148 pages
publisher
Malin Bydén Sjöbom, Dept. of Natural and Environmental Sciences, Mid Sweden University, SE-851 70 Sundsvall, Sweden,
defense location
SCA-salen (O102), Mid Sweden University, Sundsvall, Sweden
defense date
2002-05-17 13:00:00
ISBN
91-628-5225-6
language
English
LU publication?
yes
additional info
Article: 1. Phase Equilibria and Structure of the 1-Dodecyl Pyridinium Bromide-Dodecane-Water System. Edlund, H.; Bydén, M.; Lindström, B.; Khan, A. J. Colloid and Interface Sci. 1998, 204, 312. Article: 2. Ternary Phase Equilibria of the 1-Dodecyl Pyridinium Bromide-Dodecanol-Water System. Edlund, H.; Bydén, M.; Lindström, B.; Khan, A. J. Colloid Interface Sci. 1997, 196, 231. Article: 3. Binary Phase Equilibria and Structure of the Two a-Methylsubstituted Surfactants Sodium (R)-2-Methyldecanoate and Racemic Sodium 2-Methyldecanoate. Sjöbom, M. B.; Edlund, H.; Lindström, B. Langmuir 1999, 15, 2654. Article: 4. Binary Phase Equilibria of Three a-Methylsubstituted Sodium Alkanoate Surfactant Systems. Sjöbom, M. B.; Hedenström, E.; Edlund, H. Submitted to J. Colloid Interface Sci. Article: 5. Dependence of Alkyl Chain Asymmetry on the Phase Equilibria of Three Catanionic Surfactant Mixtures Containing Dodecyltrimethylammonium Chloride-Sodium Alkylcarboxylate-Water. Sjöbom, M. B.; Edlund, H. Submitted to Langmuir. Article: 6. Phase Equilibria of the Mixed Didodecyldimethylammonium Bromide-Sodium Taurodeoxycholate-Water System with a Large Solution Region. Sjöbom, M. B.; Marques, E. F.; Edlund, H.; Khan, A. Submitted to Langmuir.
id
dce9d3d3-8f44-47b1-a5b0-9f55d9c7c10c (old id 464586)
date added to LUP
2016-04-04 10:07:13
date last changed
2018-11-21 20:56:51
@phdthesis{dce9d3d3-8f44-47b1-a5b0-9f55d9c7c10c,
  abstract     = {{Surfactant self-assembly is an important phenomenon that occurs in a number of processes in our everyday life. It is important to understand the forces and parameters that control and influence the self-assembly, as this knowledge can be used both in order to design surfactant systems with desired properties and for creating model systems, for example for biological processes. The papers of this thesis all concern the phase equilibria of ionic surfactant systems, which have been investigated by means of &lt;sup&gt;2&lt;/sup&gt;H NMR, optical methods and SAXS.<br/><br>
<br/><br>
The aqueous ternary phase diagrams of 1-dodecylpyridinium bromide, with dodecane and dodecanol as the respective third component, were studied.<br/><br>
<br/><br>
The sodium 2-methyldecanoate was proved to have a very low Krafft-temperature in the solution phase, about 1 °C. Both the pure (R)- and the racemic surfactant formed the same phase sequence with water as have been seen for sodium decanoate, although at lower temperatures. They also form a very narrow intermediate phase, with a so far unknown structure.<br/><br>
<br/><br>
The phase equilibria of the binary aqueous systems of a-methylated sodium octanoate, -nonanoate and -dodecanoate respectively, were studied. The two former show a phase sequence very similar to sodium octanoate. The latter has a phase sequence different from its unsubstituted analog, as we have not been able to isolate any hexagonal structure, and only one intermediate phase, most likely a rhombhohedrical structure.<br/><br>
<br/><br>
In the pseudo-ternary DoTAC-sodium carboxylate-water systems, the level of asymmetry was proven to play an important role for the extension of both micellar solutions and liquid crystalline phases. The combination DoTAC-sodium octanoate seemed to be the most suitable for the formation of a mixed hexagonal structure, whereas sodium decanoate gave the largest lamellar phase. All three systems form mixed micelles at carboxylate/DoTAC molar ratios &lt;1, and coexisting aggregates or aggregates and monomers at higher ratios. Within the DoTAC-decanoate solution phase, there is a narrow coacervation area around equimolarity.<br/><br>
<br/><br>
The complete pseudo-ternary phase diagram of the DDAB-sodium taurodeoxycholate-water system was presented. The DDAB-rich side was studied by means of &lt;sup&gt;2&lt;/sup&gt;H NMR and SAXS, whereas NMR self-diffusion measurements were performed in the large solution phase. The latter results indicate that the solution phase is consistent of aggregates with positive curvature throughout its whole range of existence.}},
  author       = {{Bydén Sjöbom, Malin}},
  isbn         = {{91-628-5225-6}},
  keywords     = {{coacervation; asymmetry; bile salt; didodecyldimethylammonium bromide; Physical chemistry; Fysikalisk kemi; catanionic surfactant mixture; intermediate phase; a-methylsubstituted sodium carboxylate; dodecylpyridinium bromide; ionic surfactant; polarizing microscopy; FT-PGSE self-diffusion; 2H NMR; SAXS; liquid crystal; micelle; phase equilibria; phase diagram}},
  language     = {{eng}},
  publisher    = {{Malin Bydén Sjöbom, Dept. of Natural and Environmental Sciences, Mid Sweden University, SE-851 70 Sundsvall, Sweden,}},
  school       = {{Lund University}},
  title        = {{Catanionic Surfactant Mixtures and Binary Systems of Modified Fatty Acid Surfactants. Phase Equilibria and Structure.}},
  year         = {{2002}},
}