Microdroplet Technology Based Functional Microcapsules Generation, Handling and Applications

制度:新 ; 報告番号:甲3593号 ; 学位の種類:博士(工学) ; 授与年月日:2012/2/25 ; 早大学位記番号:新593

Design and synthesis of microcapsules using microfluidics for autonomic self-healing in cementitious materials

A capsule-based self-healing cementitious material, capable of autonomically repairing its own cracks, can extend the service life of concrete structures and decrease the costs associate with repair and maintenance actions. However, the size, shell thickness, shell material and mechanical properties of the capsules still need to be optimised to ensure self-healing performance. Thus, the objective of this research was to explore the controlled microfluidic encapsulation to investigate the production of microcapsules for physically triggered self-healing in cementitious materials. A flow-focusing microfluidic device was used to produce double emulsions to be selectively photopolymerised to generate a core-shell structure. Subsequently, the physical triggering was assessed by embedding the produced microcapsules in cement paste, fracturing it and observing the cracked surface in the SEM. The results showed the production of microcapsules with 80-140 μm of diameter with excellent control over size and shell thickness. Using water-in-oil-in-water (w/o/w) double emulsion, microcapsules were synthesised containing water, colloidal silica solution and sodium silicate solution as core material. In addition, an oil-in-oil-in-water (o/o/w) double emulsion was used to encapsulate mineral oil and emulsified healing agents. The formation of the core-shell structure with aqueous and organic cores was characterised using optical microscopy and SEM. It was demonstrated that the water is not retained inside of the capsule, resulting in the formation of dimples and buckled capsules, particularly for shells thickness ~7 μm. On the other hand, TGA confirmed the retention of mineral oil for shells thickness of ~2 μm and the encapsulation efficiency was demonstrated to be 66%. When the capsules were added to the cement paste, four key factors were observed to prevent physical triggering: (i) thick shells, (ii) buckling of thinner shells due to the loss of water core, (iii) mechanical properties and (iv) poor interfacial bonding. As a result, a mechanical characterisation of the shell material was performed, indicating brittle fracture at room temperature, reduced Young’s modulus when compared with cementitious matrix and stress at rupture of 15-36 MPa. In addition, an innovative methodology was proposed to functionalise the surface of the microcapsules with hydrophilic groups in order to increase the interfacial bonding between the cement paste and the microcapsules. Thus, microcapsules with low tensile strength, low shell thickness, organic core and good interfacial bonding were successfully synthesised and demonstrated to rupture upon crack formation. These results experimentally demonstrate the importance of reduced shell thickness, core retention and interfacial bonding as valuable guides during the design of microcapsules for physically triggered self-healing in cementitious materials.Science without Borders/Brazil (BEX 9185/13-5

“On-The-Fly” Fabrication of Highly-Ordered Interconnected Cylindrical and Spherical Porous Microparticles via Dual Polymerization Zone Microfluidics

A microfluidic platform with dual photopolymerization zones has been developed for production of novel uniform interconnected porous particles with shapes imposed either by the geometry of the external capillary or by the thermodynamic minimisation of interfacial area. Double w/o/w drops with well-defined internal droplet size and number were produced and then exposed to online photopolymerization to create the porous particles. Cylindrical interconnected porous particles were produced in a segmented flow where the drops took the shape of the capillary. The microfluidic set up included an extension capillary where the drops relaxed and conformed to their thermodynamically favoured morphology. Window opening of the particles occurred “on-the-fly” during UV polymerization without using any offline auxiliary methods. A distinction was made between critically and highly packed arrangements in double drops. The window opening occurred consistently for highly packed spherical drops, but only for critically packed drops containing more than 6 internal cores at internal phase ratio as low as 0.35. The size and number of cores, shape and structure of double drops could be precisely tuned by the flowrate and by packing structure of the inner droplets

Microfluidic production of multiple emulsions

Microfluidic devices are promising tools for the production of monodispersed tuneable complex emulsions. This review highlights the advantages of microfluidics for the fabrication of emulsions and presents an overview of the microfluidic emulsification methods including two-step and single-step methods for the fabrication of high-order multiple emulsions (double, triple, quadruple and quintuple) and emulsions with multiple and/or multi-distinct inner cores. The microfluidic methods for the formation of multiple emulsion drops with ultra-thin middle phase, multi-compartment jets, and Janus and ternary drops composed of two or three distinct surface regions are also presented. Different configurations of microfluidic drop makers are covered, such as co-flow, T-junctions and flow focusing (both planar and three-dimensional (3D)). Furthermore, surface modifications of microfluidic channels and different modes of droplet generation are summarized. Non-confined microfluidic geometries used for buoyancy-driven drop generation and membrane integrated microfluidics are also discussed. The review includes parallelization and drop splitting strategies for scaling up microfluidic emulsification. The productivity of a single drop maker is typically 1 L/h, which requires combining drop makers into twodimensional (2D) and 3D assemblies fed from a single set of inlet ports through a network of distribution and collection channel

Advances in Optofluidics

Optofluidics a niche research field that integrates optics with microfluidics. It started with elegant demonstrations of the passive interaction of light and liquid media such as liquid waveguides and liquid tunable lenses. Recently, the optofluidics continues the advance in liquid-based optical devices/systems. In addition, it has expanded rapidly into many other fields that involve lightwave (or photon) and liquid media. This Special Issue invites review articles (only review articles) that update the latest progress of the optofluidics in various aspects, such as new functional devices, new integrated systems, new fabrication techniques, new applications, etc. It covers, but is not limited to, topics such as micro-optics in liquid media, optofluidic sensors, integrated micro-optical systems, displays, optofluidics-on-fibers, optofluidic manipulation, energy and environmental applciations, and so on

Bilayer Approaches for Nanoparticle Phase Transfer

Nanoparticles (NPs) are often synthesized in organic solvents due to advantages of superior size and shape control obtainable in a non-polar environment. However, many applications featuring NPs require them to be in aqueous media. To transfer NPs from oil to water, surfactants with amphiphilic (hydrophobic and hydrophilic) groups have been widely used. A popular phase-transfer approach involves formation of oil-in-water emulsions upon which the oil storing the NPs is boiled off. In the process, surfactants form bilayers with hydrophobic groups on the NPs rendering them water-dispersible. This transfer route however is limited in that NPs aggregate to form clusters which results in poor colloidal stability and for the specific case of quantum dots (QDs), adversely impacts optical properties. It has ever since remained a challenge to devise approaches that transfer NPs from oil to water as single particles without compromising NP stability and properties. We have discovered that by simple addition of salt to water during the step of emulsion formation, NP transfer efficiency can be greatly enhanced in "salty-micelles" of surfactants. The strength of this approach lies in its simplicity and generic nature in that the transfer scheme is valid for different NP, surfactant and salt types. Using a model system with cadmium selenide (CdSe) QDs as NPs, Aerosol-OT (AOT) as the surfactant and NaCl as the salt in water, we found >90% of CdSe QDs transferred in salty-micelles of AOT which was significantly higher than the 45-55% QDs that transferred in deionized-water (DI-water) micelles of AOT. In the salty-micelle environment, QDs were found to exist predominantly as single NPs with narrow size distribution, as established by light scattering, analytical ultracentrifugation and electron microscopy. The effects of salt were in lowering aqueous solubility of AOT through "salting-out" action and in screening repulsions between like-charged head groups of AOT molecules. Electrophoresis, thermogravimetric analysis and photoluminescence measurements using a solvatochromic dye established higher surfactant coverage with greater lateral compaction for QDs in salty-micelles over the DI-micelle counterpart. Single NP characteristics along with a hydrophobic environment in laterally compact salty-micelles resulted in better retention of optical properties of QDs. Observations of a secondary effect by salt in inducing spontaneous emulsification of a hydrocarbon (octane)/AOT/brine system were systematically investigated by tracking time-variant octane droplet size and charge. Salinity levels that determine the spontaneous curvature and phase behavior of AOT were seen to influence the initial nucleation of octane droplets and their subsequent growth. The smallest octane drops (sub 50 nm) were nucleated at the optimum cross-over salinity and emergence of the liquid crystalline phase of AOT resulted in slowest growth rates. These factors contributed towards higher transfer efficiency of NPs in salty-micelles. Two applications from formulating aqueous NP suspensions by the new phase-transfer approach are described. In the first, QD and carbon-dot (C-Dot) "nanoreporters" were formulated for oil-field reservoir characterization using Neodol 91-7 (nonionic) and Avanel S150 CGN (hybrid nonionic and anionic) as surfactants. These NPs were stable to aggregation under reservoir-representative conditions (salinities: 1M NaCl, 1M KCl and 0.55M synthetic seawater; temperatures: 70-100 °C) and demonstrated flow and transport through crushed-calcite and quartz-sand columns with high breakthrough and recovery (> 90%). In the second application, tandem assembly of a cationic polymer, multivalent salt, and NPs was investigated in a microfluidic channel where charge ratio of the polymer/salt and shear from flow and device geometry determined their assembly into higher ordered structures such as gels and capsules

Novel procedures for the production of multi-compartmental biodegradable polymeric Microneedles

The aim of this work is a new stamp based method to fabricate multi-compartmental polymeric microneedles containing a model drug

BioMEMS

As technological advancements widen the scope of applications for biomicroelectromechanical systems (BioMEMS or biomicrosystems), the field continues to have an impact on many aspects of life science operations and functionalities. Because BioMEMS research and development require the input of experts who use different technical languages and come from varying disciplines and backgrounds, scientists and students can avoid potential difficulties in communication and understanding only if they possess a skill set and understanding that enables them to work at the interface of engineering and biosciences. Keeping this duality in mind throughout, BioMEMS: Science and Engineering Perspectives supports and expedites the multidisciplinary learning involved in the development of biomicrosystems. Divided into nine chapters, it starts with a balanced introduction of biological, engineering, application, and commercialization aspects of the field. With a focus on molecules of biological interest, the book explores the building blocks of cells and viruses, as well as molecules that form the self-assembled monolayers (SAMs), linkers, and hydrogels used for making different surfaces biocompatible through functionalization. The book also discusses: Different materials and platforms used to develop biomicrosystems Various biological entities and pathogens (in ascending order of complexity) The multidisciplinary aspects of engineering bioactive surfaces Engineering perspectives, including methods of manufacturing bioactive surfaces and devices Microfluidics modeling and experimentation Device level implementation of BioMEMS concepts for different applications. Because BioMEMS is an application-driven field, the book also highlights the concepts of lab-on-a-chip (LOC) and micro total analysis system (μTAS), along with their pertinence to the emerging point-of-care (POC) and point-of-need (PON) applications

Glassy Materials Based Microdevices

Microtechnology has changed our world since the last century, when silicon microelectronics revolutionized sensor, control and communication areas, with applications extending from domotics to automotive, and from security to biomedicine. The present century, however, is also seeing an accelerating pace of innovation in glassy materials; as an example, glass-ceramics, which successfully combine the properties of an amorphous matrix with those of micro- or nano-crystals, offer a very high flexibility of design to chemists, physicists and engineers, who can conceive and implement advanced microdevices. In a very similar way, the synthesis of glassy polymers in a very wide range of chemical structures offers unprecedented potential of applications. The contemporary availability of microfabrication technologies, such as direct laser writing or 3D printing, which add to the most common processes (deposition, lithography and etching), facilitates the development of novel or advanced microdevices based on glassy materials. Biochemical and biomedical sensors, especially with the lab-on-a-chip target, are one of the most evident proofs of the success of this material platform. Other applications have also emerged in environment, food, and chemical industries. The present Special Issue of Micromachines aims at reviewing the current state-of-the-art and presenting perspectives of further development. Contributions related to the technologies, glassy materials, design and fabrication processes, characterization, and, eventually, applications are welcome