Preparation and attachment of liquid-infused porous supra-particles to liquid interfaces

© 2016 The Royal Society of Chemistry. We prepared model porous composite supra-particles and investigated the effect of the initial infused fluid phase on their attachment at the liquid-fluid interface. We used a simple method for fabrication of millimetre-sized spherical porous supra-particles from much smaller monodisperse latex microparticles as building blocks by evaporation of a polystyrene sulphate latex suspension on a hot super-hydrophobic surface. We annealed the dried supra-particles at the polymer's glass transition temperature to fuse partially their latex particle building blocks. Spherical porous supra-particles were produced above 40 wt% initial concentration of the latex particles in the suspension, which had a rough surface, with a porous and amorphous structure. We controlled the supra-particle size by varying the initial volume of the latex suspension drop, the latex particle concentration and the drop evaporation temperature. This preparation technique allowed limited control over the porosity of the supra-particles by varying the initial concentration of the latex particle suspension, the rate of evaporation and the annealing temperature. We characterised the surface morphology and the inner structure of supra-particles by SEM imaging. We report for the first time results of an MRI study of supra-particles attached to an air-water or an oil-water interface, which indicated that only the surface layer of the building block particles attaches to the liquid interface while the pore fluid was not displaced by the outer fluid. We observed that supra-particles infused with water had different wettability and attachment positions at the oil-water interface compared with the same particles infused with oil. Similarly, the infusion of the porous supra-particles with water led to a different attachment at the air-water interface compared to the attachment of the same supra-particle when dry. The fundamental importance of this result is that the porous particles (or colloid particle agglomerates) may give an oil-in-water or water-in-oil Pickering emulsion depending on whether they are initially impregnated with oil or water. The results of this study are relevant for particle-stabilised emulsions and foams in a range of pharmaceutical, food and cosmetic formulations as well as ore flotation

Attachment of composite porous supra-particles to air–water and oil–water interfaces: theory and experiment

We developed and tested a theoretical model for the attachment of fluid-infused porous supra-particles to a fluid–liquid interface. We considered the wetting behaviour of agglomerated clusters of particles, typical of powdered materials dispersed in a liquid, as well as of the adsorption of liquid-infused colloidosomes at the liquid–fluid interface. The free energy of attachment of a composite spherical porous supra-particle made from much smaller aggregated spherical particles to the oil–water interface was calculated. Two cases were considered: (i) a water-filled porous supra-particle adsorbed at the oil–water interface from the water phase, and, (ii) an oil-filled porous supra-particle adsorbed at the oil–water interface from the oil-phase. We derived equations relating the three-phase contact angle of the smaller “building block” particles and the contact angle of the liquid-infused porous supra-particles. The theory predicts that the porous supra-particle contact angle attached at the liquid interface strongly depends on the type of fluid infused in the particle pores and the fluid phase from which it approaches the liquid interface. We tested the theory by using millimetre-sized porous supra-particles fabricated by evaporation of droplets of polystyrene latex suspension on a pre-heated super-hydrophobic surface, followed by thermal annealing at the glass transition temperature. Such porous particles were initially infused with water or oil and approached to the oil–water interface from the infusing phase. The experiment showed that when attaching at the hexadecane–water interface, the porous supra-particles behaved as hydrophilic when they were pre-filled with water and hydrophobic when they were pre-filled with hexadecane. The results agree with the theoretically predicted contact angles for the porous composite supra-particles based on the values of the contact angles of their building block latex particles measured with the Gel Trapping Technique. The experimental data for the attachment of porous supra particles to the air–water interface from both air and water also agree with the theoretical model. This study gives important insights about how porous particles and particle aggregates attach to the oil–water interface in Pickering emulsions and the air–water surface in particle-stabilised aqueous foams relevant in ore flotation and a range of cosmetic, pharmaceutical, food, home and personal care formulations

Adsorption of carboxylic modified latex particles at liquid interfaces studied by the gel trapping technique

We have studied how carboxylic modified latex (CML) microparticles adsorb at liquid surfaces and the preferred type of emulsion they can stabilise depending on the particle size and the surface density of carboxylic groups. We measured the particle contact angle by using the gel trapping technique (GTT) for CML particles adsorbed at air–water and oil–water interfaces. Using this method we obtained scanning electron microscopy (SEM) micrographs of polydimethylsiloxane (PDMS) replicas of the liquid interface with the particles, where the PDMS replicates the non-polar phase and measured the particle contact angle. We discovered that the particle wettability correlates well with the surface density of the carboxylic groups but is not very sensitive to the presence of electrolyte in the aqueous phase and the value of the particle zeta potential. We demonstrated that CML microparticles with a high surface density of COOH groups stabilise oil-in-water (O/W) emulsions while those with the lowest coverage of COOH groups favour the formation of water-in-oil (W/O) emulsions. We found that this corresponds to a change of the CML particle contact angle from lower than 90° to higher than 90° upon decrease of the surface density of COOH groups. The findings confirm that the surface density of polar groups has a much bigger effect on the particle wettability and the preferred emulsion than the particle surface charge and zeta potential. Our results on the type of stabilised Pickering emulsion agree with other experimental studies with different particle materials. We propose an alternative explanation for the link between the particle contact angle and the type of stabilised Pickering emulsion

Tensile and fracture behaviour of isotropic and die-drawn polypropylene-clay nanocomposites. Compounding, processing, characterization and mechanical properties of isotropic and die-drawn polypropylene/clay/polypropylene maleic anhydride composites

As a preliminary starting point for the present study, physical and mechanical properties of polypropylene nanocomposites (PPNCs) for samples received from Queen's University Belfast have been evaluated. Subsequently, polymer/clay nanocomposite material has been produced at Bradford. Mixing and processing routes have been explored, and mechanical properties for the different compounded samples have been studied. Clay intercalation structure has received particular attention to support the ultimate objective of optimising tensile and fracture behaviour of isotropic and die-drawn PPNCs. Solid-state molecular orientation has been introduced to PPNCs by the die-drawing process. Tensile stress-strain measurements with video-extensometry and tensile fracture of double edge-notched tensile specimens have been used to evaluate the Young¿s modulus at three different strain rates and the total work of fracture toughness at three different notch lengths. The polymer composite was analyzed by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, wide angle x-ray diffraction, and transmission electron microscopy. 3% and 5% clay systems at various compatibilizer (PPMA) loadings were prepared by three different mixing routes for the isotropic sheets, produced by compression moulding, and tensile bars, produced by injection moulding process. Die-drawn oriented tensile bars were drawn to draw ratio of 2, 3 and 4. The results from the Queen's University Belfast samples showed a decrement in tensile strength at yield. This might be explained by poor bonding, which refers to poor dispersion. Voids that can be supported by intercalated PP/clay phases might be responsible for improvement of elongation at break. The use of PPMA and an intensive mixing regime with a two-step master batch process overcame the compatibility issue and achieved around 40% and 50% increase in modulus for 3% and 5% clay systems respectively. This improvement of the two systems was reduced after drawing to around 15% and 25% compared with drawn PP. The work of fracture is increased either by adding nanoclay or by drawing to low draw ratio, or both. At moderate and high draw ratios, PPNCs may undergo either an increase in the size of microvoids at low clay loading or coalescence of microvoids at high clay loading, eventually leading to an earlier failure than with neat PP. The adoption of PPMA loading using an appropriate mixing route and clay loading can create a balance between the PPMA stiffness effect and the degree of bonding between clay particles and isotropic or oriented polymer molecules. Spherulites size, d-spacing of silicate layers, and nanoparticles distribution of intercalated microtactoids with possible semi-exfoliated particles have been suggested to optimize the final PPNCs property.SABI

COMPARATIVE STUDY OF MULLIGAN (SNAGS) AND MAITLAND MOBILIZATION IN NECK PAIN

Objectives: Comparative Study of Mulligan (SNAGs) and Maitland’s Mobilization in Neck Pain. Design: Randomized Control Trial. Methodology: A total of 50 patients were included as per pre define inclusion and exclusion criteria and randomly assigned into two groups each having 25 patients. Group A was given conventional therapy (Active, Isometrics exercises, moist hot packs) plus SNAG while Group B was given conventional therapy (Active, Isometrics exercises, moist hot packs) plus Maitland’s mobilization for 4 weeks, 3 sessions per week one session per day. The patient’s outcome measures were assessed by visual analog scale, NDI (Neck disability Index) and Goniometry for Cervical Range of Motion. Pre and post treatment values were recorded for comparison of results. Results: Results revealed that means and S.D of both group were clinically significant but statically the Group of patients treated with conventional therapy plus SNAGS managed pain (pre=4.25±1.6, post=2.35±0.3), NDI (pre= 15.81±2.5, post= 8.18±1.7) and range of motion (flexion pre=48.9±8.9, post=53.9±4.9, extension pre=55±4.1, post=63.9±3.1, Rt side flexion pre=38.5±2.1, post=43.1±2.0 and lt. side flexion pre=38.5±2.1, post=43.6±1.8, Rt side rotation pre= 61.7±6.3, post=65.7±5.5) lt. side rotation pre=60.5±3.01, post=67.6±3.5) is not better than group of patient treated with conventional therapy plus Maitland’s mobilization in terms of pain (pre=4.27±1.5, post=1.73±0.19), NDI (pre=17.1±3.31, post=8.10±1.10) and range of motion (flexion pre=48.5±4.7, post=56.7±6.5,extension pre=57.1±4.8, post=67.9±3.9, Rt side flexion pre=35.6±2.9 post=43.1±2.2, lt Side flexion pre=38.1±2.1, post=42.5±2.0, Rt side rotation pre=58.5±5.5 post=67.1.±5.4, lt Side rotation pre=59.6±5.6, post=67.7±4.3. Conclusion: The result of study suggests that both SNAG and Maitland’s improves the symptoms of Neck pain. Better improvement was shown by Maitland’s group than SNAGs group. Based on these results Maitland mobilization with conventional therapy should be the treatment of choice for Neck pain rather than SNAGs with conventional therapy.  Article visualizations

Predictors of Cardiac Resynchronization Therapy Response: The Pivotal Role of Electrocardiogram

Heart failure affects millions of patients all over the world, and its treatment is a major clinical challenge. Cardiac dyssynchrony is common among patients with advanced heart failure. Resynchronization therapy is a major advancement in heart failure management, but unfortunately not all patients respond to this therapy. Hence, many diagnostic tests have been used to predict the response and prognosis after cardiac resynchronization therapy. In this paper we summarize the usefulness of different diagnostic modalities with special emphasis on the role of surface electrocardiogram as a major predictor of response to cardiac resynchronization therapy

Capacitor placement in distribution systems, a new formulation

Two formulations of capacitor placement problem (CPP) are presented. One is based on capacitors/losses cost balance. The other is based on comprehensive cost evaluation of network performance post CP. GA based program is implemented to solve CPP. Proposed solution technique is tested on 69-bus system reported in the literature. In addition, impact of capacitor installation on fault level and network resonance is investigated

Hydrogen storage in depleted gas reservoirs: A comprehensive review

Hydrogen future depends on large-scale storage, which can be provided by geological formations (such as caverns, aquifers, and depleted oil and gas reservoirs) to handle demand and supply changes, a typical hysteresis of most renewable energy sources. Amongst them, depleted natural gas reservoirs are the most cost-effective and secure solutions due to their wide geographic distribution, proven surface facilities, and less ambiguous site evaluation. They also require less cushion gas as the native residual gases serve as a buffer for pressure maintenance during storage. However, there is a lack of thorough understanding of this technology. This work aims to provide a comprehensive insight and technical outlook into hydrogen storage in depleted gas reservoirs. It briefly discusses the operating and potential facilities, case studies, and the thermophysical and petrophysical properties of storage and withdrawal capacity, gas immobilization, and efficient gas containment. Furthermore, a comparative approach to hydrogen, methane, and carbon dioxide with respect to well integrity during gas storage has been highlighted. A summary of the key findings, challenges, and prospects has also been reported. Based on the review, hydrodynamics, geochemical, and microbial factors are the subsurface\u27s principal promoters of hydrogen losses. The injection strategy, reservoir features, quality, and operational parameters significantly impact gas storage in depleted reservoirs. Future works (experimental and simulation) were recommended to focus on the hydrodynamics and geomechanics aspects related to migration, mixing, and dispersion for improved recovery. Overall, this review provides a streamlined insight into hydrogen storage in depleted gas reservoirs

Adsorption of shape-anisotropic and porous particles at the air–water and the decane–water interface studied by the gel trapping technique

We have studied the attachment and orientation of anisotropic and porous microparticles at liquid surfaces by using the gel trapping technique (GTT). This technique involves spreading of the microparticles of interest at the liquid interface, subsequent setting of the aqueous phase to a hydrogel thus "arresting" the particle positions at the liquid surface, and further replication of the hydrogel surface with curable polydymethilsiloxane (PDMS). The advantage of the GTT comes from the possibility to look at the PDMS replica with scanning electron microscopy (SEM) or atomic force microscopy (AFM), which allows even sub-micrometer particles to be studied at the air-water and the oil-water interface. Here we report our results on the adsorption of non-spherical anisotropic particles at liquid surfaces using the GTT. Although the GTT was originally designed to measure three-phase contact angles of spherical colloid particles, here we used this technique to reveal the orientation of a variety of shape-anisotropic and porous microparticles of practical interest at both the air-water and decane-water interfaces. We show results on typical attachment and orientation of needle-like (aragonite), rhombohedra-like (calcite) microcrystals, ethyl cellulose micro-rods, as well as highly porous hydrophilic and hydrophobic silica microparticles at these liquid interfaces. The results are important for understanding the adsorption behaviour of shape-anisotropic particles as well as porous microparticles which are used in industrial formulations as fillers, foam stabilisers and emulsifiers. © 2014 The Royal Society of Chemistry