Surfactant-free synthesis of sub-100 nm poly(styrene-co-divinylbenzene) nanoparticles by one-step ultrasonic assisted emulsification/polymerization

Tzirakis, M. D.; Zambail, Roman; Tan, Yong Zen; Chew, Jia Wei; Adlhart, Christian; Honciuc, Andrei

doi:10.1039/c5ra23840d

Cited by 13 publications

(16 citation statements)

References 66 publications

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“…The size of the obtained PBM microspheres decreases only very slightly with the increase in the ultrasonication time, from 80 μm at 15 s to 60 μm at 45 s. This aspect is important in understanding the effect of the ultrasonication time in controlling the size of the Pickering emulsion colloidosomes and the resulting polymer microspheres. The fact that the size of the microspheres are smaller with the increase in the ultrasonication time is an expected result, and was experimentally demonstrated in surfactant-free emulsion polymerization [ 42 ]. Moreover, it can seem that the size of the polymer microspheres depends only slightly on the ultrasonication time, but as we will see next to a much lesser extent than the on the surface and interfacial energy of the NPs, that it ultimately determines the quality and size of the microspheres (colloidosomes) obtained.…”

Section: Discussionmentioning

confidence: 99%

“…Then, the glass scintillator vial was sonicated, while cooling the vial in ice and acetone bath, for 15, 30, and 45 s at 30% amplitude with a Branson 450 Sonifier equipped with a 7 mm diameter horn, which corresponds to an effective energy input of ≈217, 435, and 652 J, respectively. The acoustic energy input was and its effect on the emulsion was discussed in detail in a previous report from our group [ 42 ]. Subsequently, the prepared Pickering emulsions were placed under the UV lamp (wavelength = 365 nm, with 4 lamps, each with an intensity = 2.2 mW/cm 2 ) for 1 h to initiate the polymerization reaction.…”

Section: Methodsmentioning

confidence: 99%

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Role of Surface Energy of Nanoparticle Stabilizers in the Synthesis of Microspheres via Pickering Emulsion Polymerization

Honciuc¹,

Negru²

2022

Nanomaterials

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Polymer microspheres are important for a variety of applications, such as ion exchange chromatography, catalyst supports, absorbents, etc. Synthesis of large microspheres can be challenging, because they cannot be obtained easily via classic emulsion polymerization, but rather by more complex methods. Here, we present a facile method for obtaining polymer microspheres, beyond 50 μm, via Pickering emulsion polymerization. The method consists in creating oil-in-water (o/w) Pickering emulsion/suspension from vinyl bearing monomers, immiscible with water, whereas silica nanoparticles (NPs), bearing glycidyl functionalities, have a stabilizing role by adsorbing at the monomer/water interface of emulsion droplets. The emulsion is polymerized under UV light, and polymer microspheres decorated with NPs are obtained. We discovered that the contact angle of the NPs with the polymer microsphere is the key parameter for tuning the size and the quality of the obtained microspheres. The contact angle depends on the NPs’ interfacial energy and its polar and dispersive contributions, which we determine with a newly developed NanoTraPPED method. By varying the NPs’ surface functionality, we demonstrate that when their interfacial energy with water decreases, their energy of adhesion to water increases, causing the curvature of the polymer/water interface to decrease, resulting in increasingly larger polymer microspheres.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Role of Surface Energy of Nanoparticle Stabilizers in the Synthesis of Microspheres via Pickering Emulsion Polymerization

Honciuc¹,

Negru²

2022

Nanomaterials

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“…The interfacial activity of JNPs arising from an intrinsic polarity contrast between two surface regions has been discussed theoretically in seminal publications. , Unfortunately, the true interfacial activity of JNPs remained elusive experimentally in the absence of molecular surfactants, which are almost always used as stabilizing agents during synthesis and are very difficult to completely remove by time-consuming serum replacement methods, such as centrifugation, dialysis, or electrodialysis. − Thereby, interference from the remnant surfactants or even quenching of the JNPs’ intrinsic amphiphilicity is likely . The synthesis of sufficient quantities of surfactant-free JNPs is necessary for understanding and harnessing the fundamental behavior of this class of materials, which forms the goal of the current effort.…”

Section: Introductionmentioning

confidence: 99%

Polarity Reversal in Homologous Series of Surfactant-Free Janus Nanoparticles: Toward the Next Generation of Amphiphiles

Chew

Honciuc

2016

Langmuir

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The ability to finely tune the amphiphilic balance of Janus nanoparticles (JNPs) could represent a step forward toward creating the next generation of solid-state amphiphiles with significant potential for applications. The inherent amphiphilicity of JNPs stemming from an intrinsic polarity contrast between two surface regions is well-acknowledged, but remained difficult to demonstrate experimentally in the absence of surfactants and stabilizers. We have designed two homologous series of surfactant-free polymeric JNPs starting from polystyrene (PS) seed nanoparticles (NPs) on which we grew Janus lobes of different sizes via seed polymerization and phase separation of the 3-(triethoxysilyl)propyl-methacrylate (3-TSPM) monomer. The two series differ only by the radical initiator used in the seed polymerization: polar ionic ammonium persulfate (APS) vs nonpolar oil-soluble 2,2'-azobis(2-methylpropionitrile) (AIBN). To compare the two series, we employed them in the emulsification of water with heptane or molten paraffin wax. A polarity reversal of the JNPs within AIBN-JNP series could be observed from the catastrophic and transitional emulsion phase inversions and occurred when the more polar lobe was larger than the nonpolar seed PS lobe. Furthermore, the AIBN-JNPs appeared to be amphiphilic and adopt preferred orientation within the monolayer at the oil/water interface. We therefore demonstrated that in the absence of surfactants the amphiphilicity of the JNPs depends not only on the relative size of the lobes, but also on the surface polarity contrast, which can be tuned by changing the nature of radical initiator.

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“…Surface-active agents are typically used to colloidally stabilize these latexes via electrostatic protection of latex particles. However, the use of these agents may lead to the generation of foams or the loss of stability under high shear rates and is environmentally unfriendly [ 18 ], which motivates coating technologists to develop new latexes.…”

Section: Introductionmentioning

confidence: 99%

The Effect of a Polymer-Stabilized Latex Cobinder on the Optical and Strength Properties of Pigment Coating Layers

Shen

Rajabi‐Abhari

et al. 2021

Polymers

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Coated paper with a porous coating layer may have enhanced light-scattering ability and thus favorable optical properties. However, the increased porosity of such a coating layer is likely to decrease the strength of the coated paper, thereby adversely affecting the quality of the paper in the printing and converting processes. In this research, polymer-stabilized (PS) latex was prepared and used as a cobinder for the pigment coating of the paper. The PS latex particles were colloidally stabilized by a 3:1 mixture of starch and polyvinyl alcohol. The influence of the PS latex cobinder on the viscosity, sedimentation, and consolidation of coating colors was investigated. In addition, the effect of the cobinder on the properties of coating layers, namely, their porosity and surface, optical, and tensile properties, was examined. The results revealed that the PS latex cobinder formed microstructures in the coating colors and affected their viscosity. The addition of PS latex also led to enhanced interactions between coating color components, which affected the consolidation of the coating color, resulting in the formation of dried coating layers with greater porosity and improved optical properties (i.e., higher brightness and opacity) relative to coatings without the PS latex cobinder. Furthermore, the addition of PS latex improved the tensile strength of the coating layers, which was attributable to the small size and the polymeric protective shell of the cobinder particles. Thus, these results show that this PS latex cobinder has the potential to be used for the production of high-quality coated paper products.

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Surfactant-free synthesis of sub-100 nm poly(styrene-co-divinylbenzene) nanoparticles by one-step ultrasonic assisted emulsification/polymerization

Cited by 13 publications

References 66 publications

Role of Surface Energy of Nanoparticle Stabilizers in the Synthesis of Microspheres via Pickering Emulsion Polymerization

Role of Surface Energy of Nanoparticle Stabilizers in the Synthesis of Microspheres via Pickering Emulsion Polymerization

Polarity Reversal in Homologous Series of Surfactant-Free Janus Nanoparticles: Toward the Next Generation of Amphiphiles

The Effect of a Polymer-Stabilized Latex Cobinder on the Optical and Strength Properties of Pigment Coating Layers

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