Porous polymers via emulsion templating: pore deformation during solidification cannot be explained by an osmotic transport
Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With th...
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Published in | Colloid and polymer science Vol. 299; no. 2; pp. 233 - 242 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
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Berlin/Heidelberg
Springer Berlin Heidelberg
01.02.2021
Springer Nature B.V Springer Verlag |
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Abstract | Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With the oil-soluble azobisisobutyronitrile (AIBN), an open-cell structure with spherical pores was obtained. However, with the water-soluble potassium peroxydisulfate (KPS), a closed-cell structure with rhombic dodecahedron-shaped pores and thick, layered pore walls was formed. In the latter case, a yet unexplained mechanism counteracts the capillary pressure arising from surface minimization: the surface area of a rhombic dodecahedron is ~ 10% larger than that of a sphere. In our previous work, we suggested that the underlying mechanism may be osmotic transport of DVB from the plateau borders to the films. We argued that this transport also explains the layered pore walls, i.e., the formation of two outer poly-DVB-rich layers and one inner polystyrene-rich layer. In order to prove or disprove this mechanism, we carried out additional experiments. However, none of those experiments corroborated our hypothesis of osmotic transport! This study provides clear experimental evidence that our previously suggested mechanism via which spherical droplets become polyhedral pores is incorrect. We will describe (a) the rationale behind the additional experiments, (b) our expectations, and (c) our findings. Last but not least, we will discuss all of this in the light of the proposed osmotic transport. |
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AbstractList | Abstract
Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With the oil-soluble azobisisobutyronitrile (AIBN), an open-cell structure with spherical pores was obtained. However, with the water-soluble potassium peroxydisulfate (KPS), a closed-cell structure with rhombic dodecahedron-shaped pores and thick, layered pore walls was formed. In the latter case, a yet unexplained mechanism counteracts the capillary pressure arising from surface minimization: the surface area of a rhombic dodecahedron is ~ 10% larger than that of a sphere. In our previous work, we suggested that the underlying mechanism may be osmotic transport of DVB from the plateau borders to the films. We argued that this transport also explains the layered pore walls, i.e., the formation of two outer poly-DVB-rich layers and one inner polystyrene-rich layer. In order to prove or disprove this mechanism, we carried out additional experiments. However, none of those experiments corroborated our hypothesis of osmotic transport! This study provides clear experimental evidence that our previously suggested mechanism via which spherical droplets become polyhedral pores is incorrect. We will describe (a) the rationale behind the additional experiments, (b) our expectations, and (c) our findings. Last but not least, we will discuss all of this in the light of the proposed osmotic transport. Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With the oil-soluble azobisisobutyronitrile (AIBN), an open-cell structure with spherical pores was obtained. However, with the water-soluble potassium peroxydisulfate (KPS), a closed-cell structure with rhombic dodecahedron-shaped pores and thick, layered pore walls was formed. In the latter case, a yet unexplained mechanism counteracts the capillary pressure arising from surface minimization: the surface area of a rhombic dodecahedron is ~ 10% larger than that of a sphere. In our previous work, we suggested that the underlying mechanism may be osmotic transport of DVB from the plateau borders to the films. We argued that this transport also explains the layered pore walls, i.e., the formation of two outer poly-DVB-rich layers and one inner polystyrene-rich layer. In order to prove or disprove this mechanism, we carried out additional experiments. However, none of those experiments corroborated our hypothesis of osmotic transport! This study provides clear experimental evidence that our previously suggested mechanism via which spherical droplets become polyhedral pores is incorrect. We will describe (a) the rationale behind the additional experiments, (b) our expectations, and (c) our findings. Last but not least, we will discuss all of this in the light of the proposed osmotic transport. sing microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With the oil-soluble azobisisobutyronitrile (AIBN), an open-cell structure with spherical pores was obtained. However, with the water-soluble potassium peroxydisulfate (KPS), a closed-cell structure with rhombic dodecahedron-shaped pores and thick, layered pore walls was formed. In the latter case, a yet unexplained mechanism counteracts the capillary pressure arising from surface minimization: the surface area of a rhombic dodecahedron is ~ 10% larger than that of a sphere. In our previous work, we suggested that the underlying mechanism may be osmotic transport of DVB from the plateau borders to the films. We argued that this transport also explains the layered pore walls, i.e., the formation of two outer poly-DVB-rich layers and one inner polystyrene-rich layer. In order to prove or disprove this mechanism, we carried out additional experiments. However, none of those experiments corroborated our hypothesis of osmotic transport! This study provides clear experimental evidence that our previously suggested mechanism via which spherical droplets become polyhedral pores is incorrect. We will describe (a) the rationale behind the additional experiments, (b) our expectations, and (c) our findings. Last but not least, we will discuss all of this in the light of the proposed osmotic transport. |
Author | Stubenrauch, Cosima Koch, Lukas Drenckhan, Wiebke |
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Cites_doi | 10.1038/nbt0794-689 10.1103/PhysRevLett.93.208301 10.1002/macp.1962.020570105 10.1016/j.cis.2015.05.004 10.1002/adem.200600167 10.1063/1.3122665 10.1002/smll.200801498 10.1002/polc.5070530113 10.1021/acs.langmuir.6b03762 10.1007/BF00655236 10.1016/j.biomaterials.2011.06.018 10.1016/S0032-3861(00)00820-X 10.1039/c1sm05371j 10.1039/b517731f 10.1021/ma00001a019 10.1209/epl/i2003-10295-7 10.1021/la303788z 10.1021/acs.macromol.6b00494 10.1039/c3tb21227k 10.1002/cphc.201600834 10.1002/adem.201500040 10.1016/j.colsurfa.2005.02.037 10.1021/la00081a027 |
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Keywords | Emulsion templating Macroporous polystyrene Microfluidics Pore deformation Osmotic transport |
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Snippet | Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing... Abstract Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When... sing microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and... |
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SubjectTerms | Azobisisobutyronitrile Capillary pressure Characterization and Evaluation of Materials Chemical Sciences Chemistry Chemistry and Materials Science Complex Fluids and Microfluidics Divinylbenzene Emulsion polymerization Experiments Food Science Invited Article Material chemistry Microfluidics Monomers Nanotechnology and Microengineering Physical Chemistry Polymer Sciences Polystyrene resins Porosity Potassium persulfate Soft and Granular Matter Solidification |
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Title | Porous polymers via emulsion templating: pore deformation during solidification cannot be explained by an osmotic transport |
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