Recent large-scale computer simulations suggest that it may be possible to create a new class of soft solids, called 'bijels', by stabilizing and arresting the bicontinuous interface in a binary liquid demixing via spinodal decomposition using particles that are neutrally wetted by both liquids. The interfacial layer of particles is expected to be semi-permeable; hence, if realized, these new materials would have many potential applications, for example, as micro-reaction media. However, the creation of bijels in the laboratory faces serious obstacles. In general, fast quench rates are necessary to bypass nucleation, so that only samples with limited thickness can be produced, which destroys the three-dimensionality of the putative bicontinuous network. Moreover, even a small degree of unequal wettability of the particles by the two liquids can lead to ill-characterized, 'lumpy' interfacial layers and therefore irreproducible material properties. Here, we report a reproducible protocol for creating three-dimensional samples of bijel in which the interfaces are stabilized by essentially a single layer of particles. We demonstrate how to tune the mean interfacial separation in these bijels, and show that mechanically, they indeed behave as soft solids. These characteristics and their tunability will be of great value for microfluidic applications.
We have investigated the spin fluctuations at energy transfers up to ∼ 110 meV, well above the resonance energy (33 meV) in the YBa2Cu3O6.5 ortho-II superconductor using neutron timeof-flight and triple-axis techniques. The spectrum at high energies differs from the low-energy incommensurate modulations previously reported where the incommensurate wave vector is largely independent of energy. Well above the resonance the peak of the spin response lies at wave vectors that increase with energy. Within error the excitations at all energies above the resonance are best described by a ring around the (π, π) position. The isotropic wave-vector pattern differs from a recently reported square pattern in different but related systems. The spin spectral weight at high-energies is similar to that in the insulator but the characteristic velocity is ∼ 40% lower. We introduce a method of extracting the acoustic and optic weights at all energies from time-of-flight data. We find that the optic spectral weight extends to surprisingly low-energies of ∼ 25 meV, and infer that the bilayer spin correlations weaken with increase in hole doping. When the low-energy optic excitations are taken into account we measure the total integrated weight around (π, π), for energies below 120 meV, to agree with that expected from the insulator. As a qualitative guide, we compare spin-wave calculations for an ordered and a disordered stripe model and describe the inadequacy of this and other stripe models for the high-energy fluctuations.
Bicontinuous, interfacially jammed emulsion gels (bijels) are a class of soft solid materials in which interpenetrating domains of two immiscible fl uids are stabilized by an interfacial colloidal monolayer. Such structures form through the arrest of the spinodal decomposition of an initially single-phase liquid mixture containing a colloidal suspension. With the use of hexalmethyldisilazane, the wetting character of silica colloids, ranging in size and dye content, can be modifi ed for fabricating a novel bijel system comprising the binary liquid ethanediol-nitromethane. Unlike the preceding water-lutidine based system, this bijel is stable at room temperature and its fabrication and resultant manipulation are comparatively straightforward. The new system has facilitated three advancements: fi rstly, we use sub 100 nm silica particles to stabilize the fi rst bijel made from low molecular weight liquids that has domains smaller than ten micrometers. Secondly, our new and robust bijel permits qualitative rheological work which reveals the bijel to be signifi cantly elastic and self healing whilst its domains are able to break, reform and locally rearrange. Thirdly, we encapsulate the ethanediol-nitromethane bijel in Pickering drops to form novel particle-stabilized bicontinuous multiple emulsions that we christen bijel capsules. These emulsions are stimuli responsive -they liberate their contained materials in response to changes in temperature and solvency, and hence they show potential for controlled release applications.
We have created strongly aggregating Pickering emulsions using our model system. This aggregating state can be accessed by varying several different parameters, including particle wettability and particle volume fraction. Particles with a slight preference for the continuous phase are required for bridging to occur, and the degree of bridging increases with increasing shear rate but decreases with increasing particle volume fraction. Particle bridges can subsequently be removed by applying low shear or by modifying the particle wettability.
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