Transferring Micellar Changes to Bulk Properties via Tunable Self-Assembly and Hierarchical Ordering.

Hierarchical self-assembly is an effective means of preparing useful materials. However, control over assembly across length scales is a difficult challenge, often confounded by the perceived need to redesign the molecular building blocks when new material properties are needed. Here, we show that we can treat a simple dipeptide building block as a polyelectrolyte and use polymer physics approaches to explain the self-assembly over a wide concentration range. This allows us to determine how entangled the system is and therefore how it might be best processed, enabling us to prepare interesting analogues to threads and webs, as well as films that lose order on heating and "noodles" which change dimensions on heating, showing that we can transfer micellar-level changes to bulk properties all from a single building block.

Surface Tension and Viscosity Dependence of Slip Length over Irregularly Structured Superhydrophobic Surfaces.

A comprehensive understanding of the slip phenomenon on liquid/solid interfaces is essential for multiple real-world applications of superhydrophobic materials, especially those involving drag reduction. In the current contribution, the so-called "slip-length" on an irregularly structured superhydrophobic surface was systematically evaluated, with respect to varying liquid surface tension and viscosity. The superhydrophobic polymer-nanoparticle composite (SPNC) material used exhibits a dual-scale surface roughness and was fabricated via coating a surface with a mixture of polydimethylsiloxane solution and functionalized silica particles. A cone-and-plate rheometric device was employed to quantify the slip length. To independently study the impact of surface tension and viscosity, three types of aqueous solutions were used: sodium dodecyl sulfate, ethanol, and polyethylene glycol. Our experimental results demonstrate that a decreasing surface tension results in a decreasing slip length when the fluid viscosity is held constant. Meanwhile, the slip length is shown to increase with increasing viscosity when the surface tension of the various liquids is matched to isolate effects. The study reveals a linear relationship between slip length and both capillary length and viscosity providing a reference to potentially predict the degree of achievable drag reduction for differing fluids on SPNC surfaces.

Charge screening wormlike micelles affects extensional relaxation time and noodle formation.

A functionalised dipeptide that self-assembles to form wormlike micelles at high pH can be treated as a surfactant. By varying salt concentration, the self-assembled structures and interactions between them change, resulting in solutions with very different shear and extensional viscosity. From these, gel noodles with different mechanical properties can be prepared.

Low- and High-Drag Intermittencies in Turbulent Channel Flows.

Recent direct numerical simulations (DNS) and experiments in turbulent channel flow have found intermittent low- and high-drag events in Newtonian fluid flows, at Reτ=uτh/ν between 70 and 100, where uτ, h and ν are the friction velocity, channel half-height and kinematic viscosity, respectively. These intervals of low-drag and high-drag have been termed "hibernating" and "hyperactive", respectively, and in this paper, a further investigation of these intermittent events is conducted using experimental and numerical techniques. For experiments, simultaneous measurements of wall shear stress and velocity are carried out in a channel flow facility using hot-film anemometry (HFA) and laser Doppler velocimetry (LDV), respectively, for Reτ between 70 and 250. For numerical simulations, DNS of a channel flow is performed in an extended domain at Reτ = 70 and 85. These intermittent events are selected by carrying out conditional sampling of the wall shear stress data based on a combined threshold magnitude and time-duration criteria. The use of three different scalings (so-called outer, inner and mixed) for the time-duration criterion for the conditional events is explored. It is found that if the time-duration criterion is kept constant in inner units, the frequency of occurrence of these conditional events remain insensitive to Reynolds number. There exists an exponential distribution of frequency of occurrence of the conditional events with respect to their duration, implying a potentially memoryless process. An explanation for the presence of a spike (or dip) in the ensemble-averaged wall shear stress data before and after the low-drag (or high-drag) events is investigated. During the low-drag events, the conditionally-averaged streamwise velocities get closer to Virk's maximum drag reduction (MDR) asymptote, near the wall, for all Reynolds numbers studied. Reynolds shear stress (RSS) characteristics during these conditional events are investigated for Reτ = 70 and 85. Except very close to the wall, the conditionally-averaged RSS is higher than the time-averaged value during the low-drag events.

Controlling the properties of the micellar and gel phase by varying the counterion in functionalised-dipeptide systems.

The micellar aggregates formed at high pH for dipeptide-based gelators can be varied by using different alkali metal salts to prepare the solutions. The nature of the micellar aggregates directly affects the properties of the resulting gels.

3D printing with 2D colloids: designing rheology protocols to predict 'printability' of soft-materials.

Additive manufacturing (AM) techniques and so-called 2D materials have undergone an explosive growth in the past decade. The former opens multiple possibilities in the manufacturing of multifunctional complex structures, and the latter on a wide range of applications from energy to water purification. Extrusion-based 3D printing, also known as Direct Ink Writing (DIW), robocasting, and often simply 3D printing, provides a unique approach to introduce advanced and high-added-value materials with limited availability into lab-scale manufacturing. On the other hand, 2D colloids of graphene oxide (GO) exhibit a fascinating rheology and can aid the processing of different materials to develop 'printable' formulations. This work provides an in-depth rheological study of GO suspensions with a wide range of behaviours from Newtonian-like to viscoelastic 'printable' soft solids. The combination of extensional and shear rheology reveals the network formation process as GO concentration increases from <0.1 vol% to 3 vol%. Our results also demonstrate that the quantification of 'printability' can be based on three rheology parameters: the stiffness of the network via the storage modulus (G'), the solid-to-liquid transition or flow stress (σf), and the flow transition index, which relates the flow and yield stresses (FTI = σf/σy).

Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides.

A simple heat/cool cycle can be used to significantly affect the properties of a solution of a low-molecular-weight gelator at high pH. The viscosity and extensional viscosity are increased markedly, leading to materials with very different properties than when the native solution is used.

Nonlinear Effects in Multicomponent Supramolecular Hydrogels.

Multicomponent low molecular weight gels are useful for a range of applications. However, when mixing two components, both of which can independently form a gel, there are many potential scenarios. There is a limited understanding as to how to control and direct the assembly. Here, we focus on a pH-triggered two-component system. At high pH, colloidal structures are formed, and there is a degree of mixing of the two gelators. As the pH is decreased, there is a complex situation, where one gelator directs the assembly in a "sergeants and soldiers" manner. The second gelator is not fully incorporated, and the remainder forms an independent network. The result is that there is a nonlinear dependence on the final mechanical properties of the gels, with the storage or loss modulus being very dependent on the absolute ratio of the two components in the system.

The stabilizing effect of shear thinning on the onset of purely elastic instabilities in serpentine microflows.

We determine both experimentally and numerically the onset of elastic flow instabilities in viscoelastic polymer solutions with different levels of shear thinning. Previous experiments realized in microfluidic serpentine channels using dilute polymeric solutions showed that the onset of elastic instabilities strongly depends on the channel curvature. The scaling dependence is well captured by the general instability scaling criterion proposed by Pakdel and McKinley [Phys. Rev. Lett., 1996, 76, 2459:1-4]. We determine here the influence of fluid shear thinning on the onset of such purely-elastic flow instabilities. By testing a set of polyethylene oxide solutions of high molecular weight at different polymer concentrations in microfluidic serpentine channels we observe that shear thinning has a stabilizing effect on the microfluidic flow. Three-dimensional numerical simulations performed using the White-Metzner model predict similar trends, which are not captured by a simple scaling analysis using the Pakdel-McKinley criterion.

Tricritical spiral vortex instability in cross-slot flow.

We examine fluid flow through cross-slot devices with various depth to width ratios α. At low Reynolds number, Re, flow is symmetric and a sharp boundary exists between the two incoming fluid streams. Above an α-dependent critical value, Re(c)(α), a steady symmetry-breaking bifurcation occurs and a spiral vortex structure develops. Order parameters characterizing the instability grow according to a sixth-order Landau potential, and show a progression from second- to first-order transitions as α increases beyond a tricritical value of α ≈ 0.55. Flow simulations indicate the instability is driven by vortex stretching at the stagnation point.

Type IIIb Endoleak and Relining: A Mathematical Model of Distraction Forces.

PURPOSE: To examine the changes in distraction force following relining of a conventional abdominal aortic stent-graft with a type IIIb endoleak using the Nellix endovascular sealing device compared to a unilateral stent-graft. METHODS: Relining is often used to repair type IIIb endoleaks, but the consequences to graft stability are unknown. A mathematical model was constructed based on pressure and volume flow through the stent-grafts, incorporating recognized distraction force equations. Steady flow was presumed at peak systolic pressures to calculate the maximum distraction force, with gravity ignored. Distraction forces for 28- to 36-mm-diameter stent-graft bodies with 16-mm limbs were calculated and compared to forces following relining with single and double Nellix devices or the Renu unilateral device. RESULTS: Distraction forces for the 28-, 32-, and 36-mm stent-grafts prior to relining were 5.99, 10.21, and 14.99 N, respectively. Similar forces were reported after relining with bilateral Nellix devices (5.86, 10.08, and 14.86 N, respectively). However, use of a unilateral Nellix increased the distraction forces to 9.92, 14.14, and 18.92 N, respectively. These were comparable to the increase observed after relining with a Renu unilateral stent-graft (9.87, 14.09, and 18.86 N, respectively). The proportional increase in distraction force for a unilateral relining ranged from 26% to 66%, with the greatest increase noted in the smaller diameter main bodies. CONCLUSION: Relining a stent-graft with a type IIIb endoleak using bilateral Nellix devices does not increase the distraction force. However, a unilateral Nellix device or the Renu system could theoretically increase the distraction force by up to 66%, potentially risking migration and type Ia endoleak. In clinical practice, these results suggest that a relining with bilateral Nellix may have benefits over the Renu unilateral stent-graft.

Development of emulsification resistant heavier-than-water tamponades using high molecular weight silicone oil polymers.

PURPOSE: Developing new blends of heavier-than-water silicone oil tamponade agents containing high molecular weight polydimethylsiloxane polymer for use in vitreoretinal surgery. MATERIALS AND METHODS: The viscoelastic properties of heavier-than-water silicone oil blends (30.5% F6H8 + 69.5% polydimethylsiloxane) containing high molecular weight polymer additive at increasing concentrations were measured using a controlled-stress rheometer (TA Instruments Rheolyst AR 1000 N). Emulsification of the blends was induced using a sonication device and a pluronic surfactant as a strong emulsifier. The percentage emulsion area was photographed and measured using ImageJ software. In a second in vitro emulsification assessment, silicone oil blends were dispersed using a high shear homogenizer and the oil-in-water droplets were counted using a coulter counter particle analyser. RESULTS: The addition of the high molecular weight polymer increased shear viscosity and viscoelasticity of the oil blends, which were measureable and to some extent predictable. The in vitro emulsification models produced contradictory results. This demonstrates the difficulty of designing and using in vitro models to evaluate the emulsification tendency of tamponade agents in vivo. CONCLUSION: Addition of a high molecular weight polymer to heavy silicone oil can increase the viscoelasticity. These findings might contribute to the development of emulsification resistant heavy silicone oils.

Computational fluid dynamic analysis of the effect of morphologic features on distraction forces in fenestrated stent grafts.

OBJECTIVE: Secure fixation of endovascular stent grafts is essential for successful endovascular aneurysm repair. Hemodynamic distraction forces are generated by blood pressure and blood flow and act against fixation force to encourage migration that may eventually lead to late stent graft failure. The aim of this in silico study was to determine which morphologic features were associated with greater distraction force. METHODS: Computer models of 54 in situ fenestrated stent grafts were constructed from postoperative computed tomography scans by use of image processing software. Computational fluid dynamic analysis was then performed by use of a commercial finite volume solver with boundary conditions representative of peak systole. Distraction force results were obtained for each component of the stent graft. Distraction force was correlated with lumen cross-sectional area (XSA) at the inlet and outlet of components and was compared between groups of components, depending on the magnitude of four predefined angles within the aortoiliac territory that we describe in detail. RESULTS: Median total resultant distraction force (RDF) acting on the fenestrated proximal bodies was 4.8 N (1.3-15.7 N); bifurcated distal bodies, 5.6N (1.0-8.0 N); and limb extensions, 1.7 N (0.6-8.4N). Inlet XSA exhibited strong, positive correlation with total RDF in proximal body and distal body components (Spearman correlation coefficient ρ, 0.883 and 0.802, respectively). Outlet XSA exhibited a similarly strong, positive correlation with total RDF in limb extension components (ρ, 0.822). Outlet angulation ≥ 45 degrees was associated with greater total RDF in the limb extension components only (P = .004). CONCLUSIONS: For a given blood pressure, XSA was the most important morphologic determinant of total RDF. Angulation within the aorta was not large enough to influence this, whereas iliac angulation affecting outlet angulation of limb extension components was associated with significantly greater total RDF.

Closure technique after carotid endarterectomy influences local hemodynamics.

BACKGROUND: Meta-analysis supports patch angioplasty after carotid endarterectomy (CEA); however, studies indicate considerable variation in practice. The hemodynamic effect of a patch is unclear and this study attempted to elucidate this and guide patch width selection. METHODS: Four groups were selected: healthy volunteers and patients undergoing CEA with primary closure, trimmed patch (5 mm), or 8-mm patch angioplasty. Computer-generated three-dimensional models of carotid bifurcations were produced from transverse ultrasound images recorded at 1-mm intervals. Rapid prototyping generated models for flow visualization studies. Computational fluid dynamic studies were performed for each model and validated by flow visualization. Mean wall shear stress (WSS) and oscillatory shear index (OSI) maps were created for each model using pulsatile inflow at 300 mL/min. WSS of <0.4 Pa and OSI >0.3 were considered pathological, predisposing to accretion of intimal hyperplasia. The resultant WSS and OSI maps were compared. RESULTS: The four groups comprised 8 normal carotid arteries, 6 primary closures, 6 trimmed patches, and seven 8-mm patches. Flow visualization identified flow separation and recirculation at the bifurcation increased with a patch and was related to the patch width. Computational fluid dynamic identified that primary closure had the fewest areas of low WSS or elevated OSI but did have mild common carotid artery stenoses at the proximal arteriotomy that caused turbulence. Trimmed patches had more regions of abnormal WSS and OSI at the bifurcation, but 8-mm patches had the largest areas of deleteriously low WSS and high OSI. Qualitative comparison among the four groups confirmed that incorporation of a patch increased areas of low WSS and high OSI at the bifurcation and that this was related to patch width. CONCLUSIONS: Closure technique after CEA influences the hemodynamic profile. Patching does not appear to generate favorable flow dynamics. However, a trimmed 5-mm patch may offer hemodynamic benefits over an 8-mm patch and may be the preferred option.

Serpentine channels: micro-rheometers for fluid relaxation times.

We propose a novel device capable of measuring relaxation times of viscoelastic fluids as small as 1 ms. In contrast to most rheometers, which by their very nature are concerned with producing viscometric or nearly-viscometric flows, here we make use of an elastic instability that occurs in the flow of viscoelastic fluids with curved streamlines. To calibrate the rheometer we combine simple scaling arguments with relaxation times obtained from first normal-stress difference data measured in a classical shear rheometer. As an additional check we also compare these relaxation times to those obtained from Zimm theory and good agreement is observed. Once calibrated, we show how the serpentine rheometer can be used to access smaller polymer concentrations and lower solvent viscosities where classical measurements become difficult or impossible to use due to inertial and/or resolution limitations. In the absence of calibration, the serpentine channel can still be a very useful comparative or index device.

The concept of aortic replacement based on computational fluid dynamic analysis: patient-directed aortic replacement.

OBJECTIVES: Aortic replacement is based on the aortic diameter in the absence of dissection or connective tissue diseases. Frequently, a number of different aortic-to-prosthetic anastomotic positions are possible depending on patient factors and surgeon preferences. High stress on residual aortic tissue may result in aneurysm formation or aneurysmal dilatation. Utilizing a computational fluid dynamic evaluation, we aimed to define possible optimal operative interventions with regard to the extent of aortic replacement. METHODS: For proof of principle, a computational fluid dynamic (CFD) analysis, using Fluent 6.2 (Ansys UK Ltd, Sheffield, UK), was performed on a simplified ascending arch and descending aortic geometry. Wall shear stress in three dimensions was assessed for the standard operations: ascending aortic replacement, arch replacement and proximal descending aortic replacement. RESULTS: Hermiarch replacement is superior to isolated ascending aortic replacement with regard to residual stress analysis on tissues (up to a 10-fold reduction). Aortic arch replacement with island implantation of the supra-aortic vessels may potentially result in high stress on the residual aorta (10-fold increase). Aortic arch replacement with individual supra-aortic vessel implantation may result in areas of high stress (10-fold increase) on native vessels if an inadequate length of supra-aortic tissue is not resected, regardless of it being aneurysmal. CONCLUSIONS: Computational fluid dynamic evaluation, which will have to be patient-specific, 3D anatomical and physiological, potentially has enormous implications for operative strategy in aortic replacement surgery. CFD analysis may direct the replacement of normal-diameter aortas in the future.

Ascending aortic curvature as an independent risk factor for type A dissection, and ascending aortic aneurysm formation: a mathematical model.

OBJECTIVE: To develop a mathematical model to demonstrate that ascending aortic curvature is an independent risk factor for type A dissections, in addition to hypertension, bicuspid aortic valve, aneurysm of ascending aorta, and intrinsic aortic tissue abnormalities, like Marfan's syndrome. METHODS: A steady state one-dimensional flow analysis was performed, utilising Newton's third law of motion. Five different clinical scenarios were evaluated: (1) effect of aortic curvature; (2) effect of beta-blockers, (3) effect of patient size, (4) forces on a Marfan's aorta, and (5) site of entry flap in aortic dissection. RESULTS: Aortic curvature increases the forces exerted on the ascending aorta by a factor of over 10-fold. Aortic curvature can cause patients with a systolic blood pressure of 8 0mmHg to have greater forces exerted on their aorta despite smaller diameters and lower cardiac outputs, than patients with systolic blood pressures of 120 mmHg. In normal diameter aortas, beta-blockers have minimal effect compared with aortic curvature. Aortic curvature may help to explain why normal diameter aortas can dissect, and also that the point of the entry tear may be potentially predictable. Aortic curvature has major effects on the forces exerted on the aorta in patients with Marfan's syndrome. CONCLUSIONS: Aortic curvature is relatively more important that aortic diameter, blood pressure, cardiac output, beta-blocker use, and patient size with regard to the force acting on the aortic wall. This may explain why some patients with normal diameter ascending aortas with or without Marfan's syndrome develop type A dissections and aneurysms. Aortic curvature may also help to explain the site of entry tear in acute type A dissection. Further clinical study is needed to validate this study's finding.