The rheological properties of Pluronic F68 were dissolved in various water/organic liquid mixtures over a wide range of temperatures, all at a concentration of 20?mg/mL. We have considered the following binary mixtures: Pluronic F68/water, F68/p-xylene, and F68/phenol. Various conformational transitions were detected and interpreted. We have also shown that these mixtures retain a Newtonian behavior independently of temperature and conformational changes. For ternary F68/p-xylene/water, F68/phenol/water, and F68/water/phenol mixtures, the behaviour of the solution is intimately related to the temperature and the amount of water and organic solvent added. 1. Introduction The triblocks copolymers based on poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), usually named Pluronics (manufactured by BASF) or Poloxamers (manufactured by ICI), are able to form direct micelles with PEO coronas and PPO cores or reverse micelles with PEO cores and PPO coronas under some conditions. The investigation of their association properties has had considerable ambiguity due to the fact that some of them are able to form direct micelles, reveres micelles, and various arrangements under several conditions, whereas some of them showed that the dimension of the structures formed was equal to the length of the hydrophobic stretched blocks [1–9]. In this regard, the critical micelle concentration, the critical micelle temperature, the aggregation number, and the polydispersity are usually given with a certain uncertainty [3]. These triblocks copolymers constitute an interesting class of surfactants which have attracted considerable attention due to their possible use in many specialized applications, for example, in the pharmaceutical industries [10] and bioprocessing [11]. In the last few years several experimental and theoretical works have been directed at the investigation of binary Pluronic/organic solvent and ternary Pluronic/water/organic solvents due to the profound changes observed in the solution properties and their wide domain of application [12–15]. Three topics characterizing these systems, namely, (i) the effect of the copolymer architecture on the association behavior [16, 17], (ii) the anomalous micellization and composition [18, 19], and (iii) the reverse micelles caused by the water presence [20], are the subject of numerous studies. For example, Ghaouar et al. [1] used dynamic light scattering and viscosity measurements for the Pluronics L64 and F68 dissolved in aqueous and organic solvent for various concentrations. To investigate their
References
[1]
N. Ghaouar, M. Ben Henda, A. Aschi, and A. Gharbi, “Study of PEO-PPO-PEO copolymers conformational changes: viscosity and dynamic light scattering measurements,” Journal of Macromolecular Science B, vol. 50, no. 11, pp. 2150–2164, 2011.
[2]
N. Ghaouar, A. Aschi, M. M. Jebari, and A. Gharbi, “Structure and thermodynamic modelling of Pluronic L64 solutions,” e-Polymers, vol. 59, no. 1, pp. 621–637, 2013.
[3]
M. M. Jebari, N. Ghaouar, A. Aschi, and A. Gharbi, “Aggregation behaviour of Pluronic L64 surfactant at various temperatures and concentrations examined by dynamic light scattering and viscosity measurements,” Polymer International, vol. 55, no. 2, pp. 176–183, 2006.
[4]
P. Alexandridis and T. A. Hatton, “Poly(ethylene oxide)poly(propylene oxide)poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure, dynamics, and modeling,” Colloids and Surfaces A, vol. 96, no. 1-2, pp. 1–46, 1995.
[5]
R. Gérard, “Micellization of block copolymers,” Progress in Polymer Science, vol. 28, no. 7, pp. 1107–1170, 2003.
[6]
M. Almgren, P. Bahadur, M. Jansson, P. Li, W. Brown, and A. Bahadur, “Static and dynamic properties of a (PEO-PPO-PEO) block copolymer in aqueous solution,” Journal of Colloid and Interface Science, vol. 151, no. 1, pp. 157–165, 1992.
[7]
C. Perreur, J.-P. Habas, J. Fran?ois, J. Peyrelasse, and A. Lapp, “Determination of the structure of the organized phase of the block copolymer PEO-PPO-PEO in aqueous solutions under flow by small-angle neutron scattering,” Physical Review E, vol. 65, no. 4, Article ID 041802, 7 pages, 2002.
[8]
A. A. Al-Saden, T. L. Whateley, and A. T. Florence, “Poloxamer association in aqueous solution,” Journal of Colloid and Interface Science, vol. 90, no. 2, pp. 303–309, 1982.
[9]
R. Nagarajan and E. Ruckenstein, “Theory of surfactant self-assembly: a predictive molecular thermodynamic approach,” Langmuir, vol. 7, no. 12, pp. 2934–2969, 1991.
[10]
C. McDonald and C. K. Wong, “The effect of temperature on the micellar properties of a polyoxypropylene polyoxyethylene polymer in water,” Journal of Pharmacy and Pharmacology, vol. 26, no. 7, pp. 556–557, 1974.
[11]
D. W. Murhammer and C. F. Goochee, “Sparged animal cell bioreactors: mechanism of cell damage and pluronic F-68 protection,” Biotechnology Progress, vol. 6, no. 5, pp. 391–397, 1990.
[12]
P. Alexandridis, U. Olsson, and B. Lindman, “A record nine different phases (four cubic, two hexagonal, and one lamellar lyotropic liquid crystalline and two micellar solutions) in a ternary isothermal system of an amphiphilic block copolymer and selective solvents (water and oil),” Langmuir, vol. 14, no. 10, pp. 2627–2638, 1998.
[13]
G. Wanka, H. Hoffmann, and W. Ulbricht, “Phase diagrams and aggregation behavior of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers in aqueous solutions,” Macromolecules, vol. 27, no. 15, pp. 4145–4159, 1994.
[14]
C. Booth and D. Attwood, “Effects of block architecture and composition on the association properties of poly(oxyalkylene) copolymers in aqueous solution,” Macromolecular Rapid Communications, vol. 21, no. 9, pp. 501–527, 2000.
[15]
S. L. Guo, T. J. Hou, and X. J. Xu, “Simulation of the phase behavior of the (EO)13(PO)30(EO)13(Pluronic L64)/water/p-xylene system using MesoDyn,” Journal of Physical Chemistry B, vol. 106, no. 43, pp. 11397–11403, 2002.
[16]
P. Alexandridis and K. Andersson, “Reverse micelle formation and water solubilization by polyoxyalkylene block copolymers in organic solvent,” Journal of Physical Chemistry B, vol. 101, no. 41, pp. 8103–8111, 1997.
[17]
P. Alexandridis, “Poly(ethylene oxide)-poly(propylene oxide) block copolymer surfactants,” Current Opinion in Colloid & Interface Science, vol. 2, no. 5, pp. 478–489, 1997.
[18]
J. Csernica, R. F. Baddour, and R. E. Cohen, “Morphological arrangements of block copolymers that result in low gas permeability,” Macromolecules, vol. 23, no. 5, pp. 1429–1433, 1990.
[19]
N. J. Jain, K. Contractor, and P. Bahadur, “Aggregation and phase behaviour of PEO/PPO/PEO block copolymers and their mixtures in water,” Journal of Surface Science and Technology, vol. 13, no. 2–4, pp. 89–98, 1997.
[20]
R. Ivanova, B. Lindman, and P. Alexandridis, “Evolution in structural polymorphism of pluronic F127 poly(ethylene oxide)-poly(propylene oxide) block copolymer in ternary systems with water and pharmaceutically acceptable organic solvents: from “glycols” to ‘oils’,” Langmuir, vol. 16, no. 23, pp. 9058–9069, 2000.
[21]
Z. Zhou and B. Chu, “Anomalous association behavior of an ethylene oxide/propylene oxide ABA block copolymer in water,” Macromolecules, vol. 20, no. 12, pp. 3089–3091, 1987.
[22]
W. Brown, K. Schillén, M. Almgren, S. Hvidt, and P. Bahadur, “Micelle and gel formation in a poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer in water solution. Dynamic and static light scattering and oscillatory shear measurements,” Journal of Physical Chemistry, vol. 95, no. 4, pp. 1850–1858, 1991.
[23]
H. Cui, Z. Chen, K. L. Wooley, and D. J. Pochan, “Controlling micellar structure of amphiphilic charged triblock copolymers in dilute solution via coassembly with organic counterions of different spacer lengths,” Macromolecules, vol. 39, no. 19, pp. 6599–6607, 2006.
[24]
X. Liang, G. Mao, and K. Y. S. Ng, “Effect of chain lengths of PEO-PPO-PEO on small unilamellar liposome morphology and stability: an AFM investigation,” Journal of Colloid and Interface Science, vol. 285, no. 1, pp. 360–372, 2005.
[25]
K. Mortensen and J. S. Pedersen, “Structural study on the micelle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer in aqueous solution,” Macromolecules, vol. 26, no. 4, pp. 805–812, 1993.
[26]
G. Wanka, H. Hoffmann, and W. Ulbricht, “The aggregation behavior of poly-(oxyethylene)-poly-(oxypropylene)-poly-(oxyethylene)-block-copolymers in aqueous solution,” Colloid & Polymer Science, vol. 268, no. 2, pp. 101–117, 1990.
[27]
K. Mortensen and W. Brown, “Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers in aqueous solution. The influence of relative block size,” Macromolecules, vol. 26, no. 16, pp. 4128–4135, 1993.
[28]
G. Gente, A. Iovino, and C. la Mesa, “Supramolecular association of a triblock copolymer in water,” Journal of Colloid and Interface Science, vol. 274, no. 2, pp. 458–464, 2004.
[29]
Z. L. Yun, R. B. Stubbersfield, and C. Booth, “Oxyethylene-oxypropylene-oxyethylene triblock copolymers crystallised from dilute solution,” European Polymer Journal, vol. 19, no. 2, pp. 107–114, 1983.
[30]
S. Borbély, “Small-angle neutron scattering study of Pluronic F68 tri-block copolymer solutions,” Physica B, vol. 241–243, pp. 1016–1018, 1997.
[31]
J. L. Newsted, “Effect of light, temperature, and pH on the accumulation of phenol by Selenastrum capricornutum, a green alga,” Ecotoxicology and Environmental Safety, vol. 59, no. 2, pp. 237–243, 2004.
[32]
Y. Kadam, B. Bharatiya, P. A. Hassan, G. Verma, V. K. Aswal, and P. Bahadur, “Effect of an amphiphilic diol (Surfynol) on the micellar characteristics of PEO-PPO-PEO block copolymers in aqueous solutions,” Colloids and Surfaces A, vol. 363, no. 1–3, pp. 110–118, 2010.
[33]
B. Bharatiya, C. Guo, J. H. Ma, P. A. Hassan, and P. Bahadur, “Aggregation and clouding behavior of aqueous solution of EO-PO block copolymer in presence of n-alkanols,” European Polymer Journal, vol. 43, no. 5, pp. 1883–1891, 2007.
[34]
R. R. Matheson Jr., “Viscosity of solutions of rigid rodlike macromolecules,” Macromolecules, vol. 13, no. 3, pp. 643–648, 1980.
[35]
Y. Kadam, R. Ganguly, M. Kumbhakar, V. K. Aswal, P. A. Hassan, and P. Bahadur, “Time dependent sphere-to-rod growth of the pluronic micelles: investigating the role of core and corona solvation in determining the micellar growth rate,” Journal of Physical Chemistry B, vol. 113, no. 51, pp. 16296–16302, 2009.
[36]
R. Ganguly, N. Choudhury, V. K. Aswal, and P. A. Hassan, “Pluronic L64 micelles near cloud point: investigating the role of micellar growth and interaction in critical concentration fluctuation and percolation,” Journal of Physical Chemistry B, vol. 113, no. 3, pp. 668–675, 2009.
[37]
P. Alexandridis, U. Olsson, and B. Lindman, “Self-assembly of amphiphilic block copolymers: the (EO)13(PO)30(EO)13-water-p-xylene system,” Macromolecules, vol. 28, no. 23, pp. 7700–7710, 1995.
[38]
G. Wu, Z. Zhou, and B. Chu, “Water-induced micelle formation of block copoly(oxyethylene-oxypropylene-oxyethylene) in o-xylene,” Macromolecules, vol. 26, no. 8, pp. 2117–2125, 1993.
[39]
J.-F. Gohy, “Block copolymer micelles,” Advances in Polymer Science, vol. 190, no. 1, pp. 65–136, 2005.
[40]
C. Doe, H.-S. Jang, S. R. Kline, and S.-M. Choi, “Subdomain structures of lamellar and reverse hexagonal pluronic ternary systems investigated by small angle neutron scattering,” Macromolecules, vol. 42, no. 7, pp. 2645–2650, 2009.
[41]
Y.-J. Huang and M. Z. Yates, “Copper etching by water-in-oil microemulsions,” Colloids and Surfaces A, vol. 281, no. 1–3, pp. 215–220, 2006.