Evolution of rheological properties of highly concentrated emulsions with aging —Emulsion-to-suspension transition
The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of 82 – 90 v % is the subject of this study. It was proven by various experimental techniques that aging leads to the emulsion-to-suspension transition. Signifi...
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| Published in | Journal of rheology (New York : 1978) Vol. 50; no. 4; pp. 435 - 451 |
|---|---|
| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
Melville, NY
The Society of Rheology
01.07.2006
Society of Rheology |
| Subjects | |
| Online Access | Get full text |
| ISSN | 0148-6055 1520-8516 |
| DOI | 10.1122/1.2206712 |
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| Abstract | The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of
82
–
90
v
%
is the subject of this study. It was proven by various experimental techniques that aging leads to the emulsion-to-suspension transition. Significant shift of rheological properties to the solid-like behavior is the result of the emulsions aging, which shows itself as an increase of the storage modules with time as well as Newtonian viscosity measured in the upward sweeping shear rate mode. Comparison of flow curves measured in the upward and downward sweeping shear rate modes shows that the rheopectic effect at low stresses is observed for both fresh and aged emulsions. Viscosity measurements in the downward mode demonstrate transition to the elastic-like behavior at low stresses with appearance of strongly pronounced yield stress. Dependencies of the characteristic rheological parameters on aging have been investigated by using different analytical methods such as optical microscope studies, differential scanning calorimetry measurements, and x-ray diffraction. All these methods showed that aging is associated with the process of slow crystallization of the dispersed droplets that comprise of overcooled highly concentrated aqueous solution, which can be considered as the main mechanism for the evolution of the emulsion's rheological properties. In this sense, the observed emulsion-to-suspension transition is the consequence of the phase transition. The kinetics of the transition process is described by the Johnson-Mehl-Avrami-Kolmogorov equation and correlates with the evolution of the rheological properties of the dispersion. |
|---|---|
| AbstractList | The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of
82
-
90
v
%
is the subject of this study. It was proven by various experimental techniques that aging leads to the emulsion-to-suspension transition. Significant shift of rheological properties to the solid-like behavior is the result of the emulsions aging, which shows itself as an increase of the storage modules with time as well as Newtonian viscosity measured in the upward sweeping shear rate mode. Comparison of flow curves measured in the upward and downward sweeping shear rate modes shows that the
rheopectic effect at low stresses is observed for both fresh and aged emulsions. Viscosity measurements in the downward mode demonstrate transition to the elastic-like behavior at low stresses with appearance of strongly pronounced yield stress. Dependencies of the characteristic rheological parameters on aging have been investigated by using different analytical methods such as optical microscope studies, differential scanning calorimetry measurements, and x-ray diffraction. All these methods showed that aging is associated with the process of slow crystallization of the dispersed droplets that comprise of overcooled highly concentrated aqueous solution, which can be considered as the main mechanism for the evolution of the emulsion's rheological properties. In this sense, the observed emulsion-to-suspension transition is the consequence of the phase transition. The kinetics of the transition process is described by the Johnson-Mehl-Avrami-Kolmogorov equation and correlates with the evolution of the rheological properties of the dispersion. The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of 82 – 90 v % is the subject of this study. It was proven by various experimental techniques that aging leads to the emulsion-to-suspension transition. Significant shift of rheological properties to the solid-like behavior is the result of the emulsions aging, which shows itself as an increase of the storage modules with time as well as Newtonian viscosity measured in the upward sweeping shear rate mode. Comparison of flow curves measured in the upward and downward sweeping shear rate modes shows that the rheopectic effect at low stresses is observed for both fresh and aged emulsions. Viscosity measurements in the downward mode demonstrate transition to the elastic-like behavior at low stresses with appearance of strongly pronounced yield stress. Dependencies of the characteristic rheological parameters on aging have been investigated by using different analytical methods such as optical microscope studies, differential scanning calorimetry measurements, and x-ray diffraction. All these methods showed that aging is associated with the process of slow crystallization of the dispersed droplets that comprise of overcooled highly concentrated aqueous solution, which can be considered as the main mechanism for the evolution of the emulsion's rheological properties. In this sense, the observed emulsion-to-suspension transition is the consequence of the phase transition. The kinetics of the transition process is described by the Johnson-Mehl-Avrami-Kolmogorov equation and correlates with the evolution of the rheological properties of the dispersion. |
| Author | Malkin, Alexander Ya Kharatiyan, Ellina Masalova, Irina Haldenwang, Rainer Ferg, Ernst Taylor, Michael |
| Author_xml | – sequence: 1 givenname: Irina surname: Masalova fullname: Masalova, Irina organization: Department of Civil Engineering, Faculty of Engineering, Cape Peninsula University of Technology, PO Box 652, Cape Town 8000, Republic of South Africa – sequence: 2 givenname: Alexander Ya surname: Malkin fullname: Malkin, Alexander Ya organization: Moscow Profoyuznaya 98, korp. 5. kv. 92, Moscow, 117485, Russia – sequence: 3 givenname: Ernst surname: Ferg fullname: Ferg, Ernst organization: Department of Chemistry, Nelson Mandela Metropolitan University, PO Box 77000, Port Elisabeth, Republic of South Africa – sequence: 4 givenname: Ellina surname: Kharatiyan fullname: Kharatiyan, Ellina organization: Department of Civil Engineering, Faculty of Engineering, Cape Peninsula University of Technology, PO Box 652, Cape Town 8000, Republic of South Africa – sequence: 5 givenname: Michael surname: Taylor fullname: Taylor, Michael organization: African Explosive Limited, Johannesburg, Republic of South Africa – sequence: 6 givenname: Rainer surname: Haldenwang fullname: Haldenwang, Rainer organization: Department of Civil Engineering, Faculty of Engineering, Cape Peninsula University of Technology, PO Box 652, Cape Town 8000, Republic of South Africa |
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| Issue | 4 |
| Keywords | Viscosity Rheopexy Sol-gel transition Aging Ammonium nitrate Viscoelastic properties Crystallinity Yield stress Water-in-oil emulsions |
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| References | Malkin, Beghishev, Keapin, Bolgov (c18) 1984a; 24 Mason (c28) 1999; 4 Boeyens, Ferg, Levendis, Schöning (c5) 1992; 44 Mason, Bibette (c27) 1996b; 77 Tadros (c41) 1994; 91 Jager-Lézer, Tranchant, Alard, Vu, Tchoreloff, Grossiord (c12) 1998; 37 Graves, Meleson, Wilking, Lin, Mason (c10) 2005; 122 Pons, Solans, Tadros (c36) 1995; 11 Dimitrova, Leal-Calderon (c7) 2004; 108–109 Langenfeld, Stébé (c15) 2002; 4 Portal, Guerrero, Berjano, Gallegos (c37) 1997; 74 Masalova, Taylor, Kharatiyan, Malkin (c24) 2005; 49 Mason, Rai (c29) 2003; 47 Hyun, Kim, Ahn, Lee (c11) 2002; 107 Pons, Solans, Stébé, Erra, Ravey (c35) 1992; 89 Masalova, Malkin, Slatter, Wilson (c23) 2003; 112 Malkin, Braverman, Plotnikova, Kulichikhin (c16) 1976; 18A Babak, Langenfeld, Fa, Stébé (c2) 2001; 118 Bower, Gallegos, Mackley, Madiedo (c6) 1999; 38 Pal (c32) 1996a; 42 Rocca, Stébé (c40) 2000; 104 Otsubo, Prud'homme (c31) 1994; 33 Langenfeld, Schmitt, Stébé (c14) 1999; 218 Malkin, Masalova, Pavlovski, Slatter (c21) 2004b; 14 Mason, Bibette, Weitz (c26) 1996a; 179 Mason, Bibette, Weitz (c25) 1995; 75 Malkin, Keapin, Bolgov, Beghishev (c19) 1984b; 46 Pal (c33) 1996b; 51 Princen, Kiss (c39) 1986; 112 Floury, Desrumaux, Lardiéres (c9) 2000; 1 Malkin, Beghishev, Keapin (c17) 1983; 24 Ferg, Levendis, Schöening (c8) 1993; 5 Malkin, Maslova, Slatter, Wilson (c20) 2004a; 43 Aronson, Ptko (c1) 1997; 159 Lacasse, Grest, Levine, Mason, Weitz (c13) 1996; 76 Pal (c34) 2000; 162 Babbete, Mason, Hu, Weitz (c3) 1992; 69 Mason, Lin (c30) 2005; 71 Otsubo, Y.; Prud'homme, R. 1994; 33 Ferg, E.; Levendis, D.; Schöening, F. 1993; 5 Rocca, S.; Stébé, M. 2000; 104 Pons, R.; Solans, C.; Tadros, Th. 1995; 11 Jager-Lézer, N.; Tranchant, J.-F.; Alard, V.; Vu, C.; Tchoreloff, P.; Grossiord, J. 1998; 37 Mason, T.; Lin, M. 2005; 71 Pal, R. 1996a; 42 Malkin, A.; Keapin, I.; Bolgov, S.; Beghishev, V. 1984b; 46 Portal, P.; Guerrero, A.; Berjano, M.; Gallegos, C. 1997; 74 Malkin, A.; Beghishev, V.; Keapin, I. 1983; 24 Mason, T.; Bibette, J.; Weitz, D. 1995; 75 Mason, T.; Bibette, J. 1996b; 77 Langenfeld, A.; Stébé, M. 2002; 4 Masalova, I.; Taylor, M.; Kharatiyan, E.; Malkin, A. 2005; 49 Mason, T.; Rai, P. 2003; 47 Bower, C.; Gallegos, C.; Mackley, M.; Madiedo, J. 1999; 38 Malkin, A.; Maslova, I.; Slatter, P.; Wilson, K. 2004a; 43 Babak, V.; Langenfeld, A.; Fa, N.; Stébé, M-J. 2001; 118 Graves, S.; Meleson, K.; Wilking, J.; Lin, M.; Mason, T. 2005; 122 Princen, H.; Kiss, A. 1986; 112 Babbete, J.; Mason, T.; Hu, G.; Weitz, D. 1992; 69 Pal, R. 2000; 162 Floury, J.; Desrumaux, A.; Lardiéres, J. 2000; 1 Dimitrova, T.; Leal-Calderon, F. 2004; 108-109 Malkin, A.; Beghishev, V.; Keapin, I.; Bolgov, S. 1984a; 24 Langenfeld, A.; Schmitt, V.; Stébé, M.-J. 1999; 218 Hyun, K.; Kim, S.; Ahn, K.; Lee, S. 2002; 107 Pons, R.; Solans, C.; Stébé, M.; Erra, P.; Ravey, J. 1992; 89 Lacasse, M.-D.; Grest, G.; Levine, D.; Mason, T.; Weitz, D. 1996; 76 Mason, T. 1999; 4 Malkin, A.; Braverman, A.; Plotnikova, E.; Kulichikhin, V. 1976; 18A Masalova, I.; Malkin, A.; Slatter, P.; Wilson, K. 2003; 112 Pal, R. 1996b; 51 Aronson, P.; Ptko, M. 1997; 159 Mason, T.; Bibette, J.; Weitz, D. 1996a; 179 Malkin, A.; Masalova, I.; Pavlovski, D.; Slatter, K. 2004b; 14 Boeyens, J.; Ferg, E.; Levendis, D.; Schöning, F. 1992; 44 Tadros, Th. 1994; 91 c31 Pons R. (c36) 1995; 11 c30 c11 c33 c10 Tadros Th. R. (c41) 1994; 91 c13 c12 Malkin A. Y. (c18) 1984; 24 c34 c39 Malkin A. Y. (c17) 1983; 24 Malkin A. Y. (c21) 2004; 14 Pons R. (c35) 1992; 89 Langenfeld A. (c14) 1999; 218 Malkin A. Ya (c16) 1976; 18 Malkin A. Y. (c19) 1984; 46 c20 Floury J. (c9) 2000; 1 c24 c23 c26 c25 c28 Pal R. (c32) 1996; 42 c27 c29 c1 c3 c6 Dimitrova T. D. (c7) 2004; 108 Boeyens J. C. A. (c5) 1992; 44 Rocca S. (c40) 2000; 104 Portal P. (c37) 1997; 74 Ferg E. E. (c8) 1993; 5 Langenfeld A. (c15) 2002; 4 Mandelkern L. (c22) 1964 Babak V. G. (c2) 2001; 118 Bampfield H. A. (c4) 1985; 7 |
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| Snippet | The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of
82
–
90
v
%
is... The effect of aging on the rheological properties and physical structure of highly concentrated water-in-oil emulsions with dispersed phase of 82 - 90 v % is... |
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| SubjectTerms | Aging Ammonium nitrate Crystallinity Rheopexy Sol-gel transition Viscoelastic properties Viscosity Water-in-oil emulsions Yield stress |
| Title | Evolution of rheological properties of highly concentrated emulsions with aging —Emulsion-to-suspension transition |
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