Increasing the Efficiency of Emulsion Crystallization in Stirred Vessels by Targeted Application of Shear and Surfactant

Emulsions containing crystalline dispersed phases hold significant importance in pharmaceutical, chemical, and life science industries. The industrial agitation and storage of these emulsions can prompt crystallization effects within the flow field, intersecting with the primary nucleation mechanisms. Notably, contact-mediated nucleation, in which subcooled droplets crystallize upon contact with a crystalline particle, and shear-induced crystallization due to droplet deformation, are both conceivable phenomena. This study delves into the crystallization processes of emulsions in a 1 L stirred vessel, integrating an ultrasonic probe to monitor droplet crystallization progression. By scrutinizing the influence of the flow field and of the emulsifiers stabilizing the droplets, our investigation unveils the direct impact of enhanced rotational speed on accelerating the crystallization rate, correlating with increased energy input. Furthermore, the concentration of emulsifiers is observed to positively affect the crystallization process. Significantly, this pioneering investigation marks the first evaluation of emulsion crystallization considering the overlapping nucleation mechanisms seen in industrial production of melt emulsions. The findings offer valuable insights for more systematic control strategies in emulsion crystallization processes, promising more efficient and sustainable industrial practices by enabling targeted application of shear and surfactants

A Microfluidic Approach to Investigate the Contact Force Needed for Successful Contact-Mediated Nucleation

Emulsions with crystalline dispersed phase fractions are becoming increasingly important in the pharmaceutical, chemical, and life science industries. They can be produced by using two-stage melt emulsification processes. The completeness of the crystallization step is of particular importance as it influences the properties, quality, and shelf life of the products. Subcooled, liquid droplets in agitated vessels may contact an already crystallized particle, leading to so-called contact-mediated nucleation (CMN). Energetically, CMN is a more favorable mechanism than spontaneous nucleation. The CMN happens regularly because melt emulsions are stirred during production and storage. It is assumed that three main factors influence the efficiency of CNM, those being collision frequency, contact time, and contact force. Not all contacts lead to successful nucleation of the liquid droplet, therefore, we used microfluidic experiments with inline measurements of the differential pressure to investigate the minimum contact force needed for successful nucleation. Numerical simulations were performed to support the experimental data obtained. We were able to show that the minimum contact force needed for CMN increases with increasing surfactant concentration in the aqueous phase

Contact-mediated nucleation of subcooled droplets in melt emulsions: A microfluidic approach

The production of melt emulsions is mainly influenced by the crystallization step, as every single droplet needs to crystallize to obtain a stable product with a long shelf life. However, the crystallization of dispersed droplets requires high subcooling, resulting in a time, energy and cost intensive production processes. Contact-mediated nucleation (CMN) may be used to intensify the nucleation process, enabling crystallization at higher temperatures. It describes the successful inoculation of a subcooled liquid droplet by a crystalline particle. Surfactants are added to emulsions/suspensions for their stabilization against coalescence or aggregation. They cover the interface, lower the specific interfacial energy and form micelles in the continuous phase. It may be assumed that micelles and high concentrations of surfactant monomers in the continuous phase delay or even hinder CMN as the two reaction partners cannot get in touch. Experiments were carried out in a microfluidic chip, allowing for the controlled contact between a single subcooled liquid droplet and a single crystallized droplet. We were able to demonstrate the impact of the surfactant concentration on the CMN. Following an increase in the aqueous micelle concentrations, the time needed to inoculate the liquid droplet increased or CMN was prevented entirely

Charge Transport and Glassy Dynamics in Blends Based on 1-Butyl-3-vinylbenzylimidazolium Bis(trifluoromethanesulfonyl)imide Ionic Liquid and the Corresponding Polymer

Charge transport, diffusion properties, and glassy dynamics of blends of imidazolium-based ionic liquid (IL) and the corresponding polymer (polyIL) were examined by Pulsed-Field-Gradient Nuclear Magnetic Resonance (PFG-NMR) and rheology coupled with broadband dielectric spectroscopy (rheo-BDS). We found that the mechanical storage modulus (G′) increases with an increasing amount of polyIL and G′ is a factor of 10,000 higher for the polyIL compared to the monomer (G′$_{IL}$= 7.5 Pa at 100 rad s$^{-1}$ and 298 K). Furthermore, the ionic conductivity (σ$_{0}$) of the IL is a factor 1000 higher than its value for the polymerized monomer with 3.4×10$^{-4}$ S cm$^{-1}$ at 298 K. Additionally, we found the Haven Ratio (H$_{R}$) obtained through PFG-NMR and BDS measurements to be constant around a value of 1.4 for the IL and blends with 30 wt% and 70 wt% polyIL. These results show that blending of the components does not have a strong impact on the charge transport compared to the charge transport in the pure IL at room temperature, but blending results in substantial modifications of the mechanical properties. Furthermore, it is highlighted that the increase in σ$_{0}$ might be attributed to the addition of a more mobile phase, which also possibly reduces ion-ion correlations in the polyIL

Influence of Shear Flow on the Crystallization of Organic Melt Emulsions – A Rheo‐Nuclear Magnetic Resonance Investigation

There is a need to better understand the influence of shear flow on the crystallization of a molten oil phase in an oil/water emulsion due to its high relevance for industrial processes. The present study focuses on the influence of laminar shear flow on the crystallization kinetics of polydisperse n ‐hexadecane‐in‐water emulsions. The investigation was carried out by rheo‐nuclear magnetic resonance (NMR) spectroscopy in a Taylor‐Couette geometry. An accelerating impact of the shear rate on the overall crystallization kinetics was verified. This effect stems from an increase of the collision frequency of already crystallized droplets with not yet crystallized droplets. Nevertheless, the collision efficiency decreased with higher shear rate

Contact-Mediated Nucleation of Subcooled Droplets in Melt Emulsions: A Microfluidic Approach

The production of melt emulsions is mainly influenced by the crystallization step, as every single droplet needs to crystallize to obtain a stable product with a long shelf life. However, the crystallization of dispersed droplets requires high subcooling, resulting in a time, energy and cost intensive production processes. Contact-mediated nucleation (CMN) may be used to intensify the nucleation process, enabling crystallization at higher temperatures. It describes the successful inoculation of a subcooled liquid droplet by a crystalline particle. Surfactants are added to emulsions/suspensions for their stabilization against coalescence or aggregation. They cover the interface, lower the specific interfacial energy and form micelles in the continuous phase. It may be assumed that micelles and high concentrations of surfactant monomers in the continuous phase delay or even hinder CMN as the two reaction partners cannot get in touch. Experiments were carried out in a microfluidic chip, allowing for the controlled contact between a single subcooled liquid droplet and a single crystallized droplet. We were able to demonstrate the impact of the surfactant concentration on the CMN. Following an increase in the aqueous micelle concentrations, the time needed to inoculate the liquid droplet increased or CMN was prevented entirely

A Microfluidic Approach to Investigate the Contact Force Needed for Successful Contact-Mediated Nucleation

Emulsions with crystalline dispersed phase fractions are becoming increasingly important in the pharmaceutical, chemical, and life science industries. They can be produced by using two-stage melt emulsification processes. The completeness of the crystallization step is of particular importance as it influences the properties, quality, and shelf life of the products. Subcooled, liquid droplets in agitated vessels may contact an already crystallized particle, leading to so-called contact-mediated nucleation (CMN). Energetically, CMN is a more favorable mechanism than spontaneous nucleation. The CMN happens regularly because melt emulsions are stirred during production and storage. It is assumed that three main factors influence the efficiency of CNM, those being collision frequency, contact time, and contact force. Not all contacts lead to successful nucleation of the liquid droplet, therefore, we used microfluidic experiments with inline measurements of the differential pressure to investigate the minimum contact force needed for successful nucleation. Numerical simulations were performed to support the experimental data obtained. We were able to show that the minimum contact force needed for CMN increases with increasing surfactant concentration in the aqueous phase