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Adhesion of a liquid droplet to a solid surface is a result of solid surface interactions with surrounding fluids, affected by its wettability and morphology. Unfortunately, the direct measurements of adhesion forces are rarely reported in the scientific literature, especially for solids with curvatures. In this study, by using a high-sensitivity microelectronic mechanical balance which vertically deposits and then pulls liquid droplets, the spreading and adhesion forces for water and ethylene glycol droplets on spherical surfaces of polyethylene terephthalate (PET) with radii of curvature from 2 to 8 mm were recorded. Results show that the surface curvature does not affect the advancing and most-stable contact angles but affects the extent of spreading and maximum adhesion forces. The solid surface curvature affects both surface tension and Laplace pressure forces at the spreading point, whereas it mainly affects the Laplace pressure force at the maximum adhesion point.
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For applications involving droplet detachment from solid surfaces, it is vital to study the droplet characteristics (e.g., contact angle and base width) when the droplet is experiencing the maximum force that detaches the droplet (maximum adhesion state). Historically, such investigations were mainly conducted on flat two-dimensional surfaces and the characteristics on curved surfaces with the third dimension remain unknown. Thus, the generalized description of such characteristics has not been established yet. Here, by vertically pulling liquid droplets using a microbalance, we study the droplet characteristics at the maximum adhesion on curved homogeneous surfaces. Variables in this study include liquid surface tension, initial droplet base area, and the asymmetry in solid surface curvature. Results show that the contact angle is identical everywhere along the droplet perimeter on curved surfaces irrespective of the asymmetry in surface curvature. In addition, we found that the droplet base is nonaxisymmetric (not circular) at the maximum adhesion, opposing previous understanding that was formulated for flat surfaces. As a result, we propose a more generalized and quantitative description of the droplet characteristics at the maximum adhesion, derived from the component of the surface tension force acting along the droplet perimeter.
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The mobility of a fakir state droplet on a structured surface is fundamentally determined by the effective length of a microscopic contact line. However, it is largely unknown how the surface topography determines the effective contact line length. Based on the direct measurement of droplet adhesion force and the visualization of contact line, this work shows that effective contact line length is topography dependent as opposed to prior notion. On pored surfaces, contact line is not distorted, and the effective length approaches the droplet apparent perimeter regardless of pore dimensions. On pillared surfaces, the distortion of contact line is significantly dependent on the packing density of the pillar structures so that the effective length is as small as a pillar diameter on densely packed pillars and as large as a pillar perimeter on sparsely-packed pillars, while changing linearly between the two extremes.
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Advances made in fabrication of patterned surfaces with well-defined dimensions of topographic features and their lateral dissemination drive the progress in interpretation of liquid spreading, adhesion, and retreat on engineered solid surfaces. Despite extensive studies on liquid droplet spreading and adhesion on textured surfaces in recent years, conformation of the three-phase contact line and its effect on macroscopic contact angle and droplet adhesion remain the focus of intensive debate. Here, we investigate the effect of surface topography on the adhesion force of Cassie-Baxter-state droplets on concentric ring-textured hydrophobic surfaces having rings with lateral dimensions of 5, 10, and 45 µm and separated by 5, 6, and 7 µm trenches, respectively, with fixed depth of 15 µm. Unlike mostly tested surfaces textured with straight ridges, pores, and pillars, where the droplet base contact line is anisotropic and its conformation varies along the apparent boundary, concentric rings are symmetrical and reinforce the microscopic contact line to align to a circular one that reflects the shape of the pattern. In this study, adhesion forces were calculated based on surface tension and Laplace pressure forces and were compared with the experimental forces for both water and ethylene glycol droplets having a varying contact diameter on the concentric ring-pattern at the point of maximum adhesion force. Results show that the microscopic contact line of the liquid retains its circular shape controlled by circular rings of the pattern, irrespectively of the droplet base diameter larger than 0.8 mm, and there is a good agreement between the experimental and calculated adhesion forces.
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The detrimental effect of natural aging on mechanical properties of zinc alloys restricts their application as bioresorbable medical implants. In this study, aging of Zn-0.05Mg alloy and the effect of 0.5 Cu and 0.1 Mn (in weight percent) addition on the microstructure and tensile properties were studied. The alloys were cold rolled, aged and annealed; aiming to investigate the effects of precipitates and grain size on the mechanical properties and their stability. TEM analysis revealed that in ultrafine-grained binary Zn-0.05Mg alloy, the natural aging occurred due to the formation of nano-sized Mg2Zn11 precipitates. After 90 days of natural aging, the yield strength and ultimate tensile strength of Zn-0.05Mg alloy increased from 197±4 MPa and 227±5 MPa to 233±8 MPa and 305±7 MPa, respectively, while the elongation was drastically reduced from 34±3% to 3±1%. This natural aging was retarded by adding the third element at either 0.1Mn or 0.5Cu quantities, which interacted with Mg in Zn solid solution and impeded the formation of Mg2Zn11 precipitates. The addition of Cu and Mn elements increased alloy's strength, ductility, and its mechanical stability at a room temperature. The measured tensile strength and elongation were 274±5 MPa and 41±1% for Zn-0.1Mn-0.05Mg and 312±2 MPa and 44±2% for Zn-0.5Cu-0.05Mg, respectively. Annealing the alloys at elevated temperatures caused increase in both grain size and dissolution of secondary phases, and both affected alloy deformation mechanisms.
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In this study, the effect of grain size and precipitates on tensile properties of Zn-1.0Cu alloy were investigated. The alloy was cold rolled and annealed to manipulate the grain size and precipitation of CuZn4 particles at grain boundaries. Cold rolling resulted in an almost ultrafinegrained structure alongside precipitation of nano-sized CuZn4 particles. Strain induced precipitates triggered room temperature superplasticity through activation of Zn/CuZn4 boundary sliding, exhibiting maximum elongation of 470% at the strain rate of 1.0 × 10-4 s-1. Short-time annealing led to significantly reduced strain rate sensitivity due to the reduction of CuZn4 fraction, while the grain size remained nearly intact. This suggests that precipitates rather than grain size mainly influence the mechanical properties of Zn alloys.
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Zinc alloy development and characterization for vascular stent application has been facilitated by many standardized and inexpensive methods. In contrast, overly simplistic in vitro approaches dominate the preliminary biological testing of materials. In 2012, our group introduced a metal wire implantation model in rats as a cost effective and realistic approach for the biocompatibility evaluation of degradable materials in the vascular environment. Here, we have adapted metrics routinely used for evaluating stents to quantitatively characterize the long-term progression of the neointima that forms around zinc based wire implants. Histological cross-sections were used to measure the length of neointimal protrusion from the wire into the lumen (denoted wire to lumen thickness), the base neointimal length (describing the breadth of neointimal activation), and the neointimal area. These metrics were used to provide in depth characterization details for neointimal responses to Zn-Mg and Zn-Li alloys and may be used to compare different materials.
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Spontaneous spreading of a droplet on a solid surface is poorly understood from a macroscopic level down to a molecular level. Here, we investigate the effect of surface topography and wettability on spontaneous spreading of a water droplet. Spreading force is measured for a suspended droplet that minimizes interference of kinetic energy in the spontaneous spreading during its contact with solid surfaces of discontinuous (pillar) and continuous (pore) patterns with various shapes and dimensions. Results show that a droplet cannot spread spontaneously on pillared surfaces regardless of their shapes or dimensions because of the solid discontinuity. On the contrary, a droplet on pored surfaces can undergo spontaneous spreading whose force increases with a decrease in the advancing contact angle. Theoretical models based on both the system free energy and capillary force along the contact line validate the direct and universal dependency of the spontaneous spreading force on the advancing contact angle.
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Increasing interest in biodegradable metals (Mg, Fe, and Zn) as structural materials for orthopedic and cardiovascular applications mainly relates to their promising biocompatibility, mechanical properties and ability to self-remove. However, Mg alloys suffer from excessive corrosion rates associated with premature loss of mechanical integrity and gas embolism risks. Fe based alloys produce voluminous corrosion products that have a detrimental effect on neighboring cells and extracellular matrix. In contrast, Zn does not appear to exhibit a harmful mode of corrosion. Unfortunately, pure zinc possesses insufficient mechanical strength for biomedical structural applications. The present study aimed at examining the potential of two new zinc based alloys, Zn-1%Mg and Zn-1%Mg-0.5%Ca to serve as structural materials for biodegradable implants. This examination was carried out under in vitro conditions, including immersion testing, potentiodynamic polarization analysis, electrochemical impedance spectroscopy (EIS), and stress corrosion cracking (SCC) assessments in terms of slow strain rate testing (SSRT). In order to assess the cytotoxicity of the tested alloys, cell viability was evaluated indirectly using Saos-2 cells. The results demonstrate that both zinc alloys can be considered as potential candidates for biodegradable implants, with a relative advantage to the Zn-1%Mg alloy in terms of its corrosion resistance and SCC performance.
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Implantes Absorvíveis , Ligas/química , Materiais Biocompatíveis/química , Cálcio/química , Magnésio/química , Zinco/química , Ligas/farmacologia , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Corrosão , Humanos , Teste de Materiais , Espectrometria por Raios X , Difração de Raios XRESUMO
Atomic force microscopy was employed to measure the colloidal interactions between silicon nitride cantilever tips and scheelite crystal surfaces in 1 mM KCl solutions of varying pH. By fitting the Derjguin-Landau-Verwey-Overbeek (DLVO) theoretical model to the recorded force-distance curves, the surface-charge density and surface-potential values were calculated for three crystallographic surfaces including {112}, {101}, and {001}. The calculated surface-potential values were negative in both acidic and basic solutions and varied among crystallographic surfaces. The determined surface-potential values were within zeta-potential values reported in the literature for powdered scheelite minerals. The surface {101} was the most negatively charged surface, followed by {112} and {001}. The surface potential for {001} was only slightly affected by pH, whereas the surface potential for both {112} and {101} increased with increasing pH. Anisotropy in surface-charge density was analyzed in relation to the surface density of active oxygen atoms, that is, the density of oxygen atoms with one or two broken bond(s) within tungstate ions located in the topmost surface layer. On a surface with a higher surface density of active oxygen atoms, a larger number of OH(-) are expected to adsorb through hydrogen bonding, leading to a more negatively charged surface.
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A new series of zinc alloys is in development for bioresorbable stent implantation to alleviate the current materials' long-term complications. Characterization and optimization of the microstructure and corresponding mechanical properties during manufacturing stages will help researchers meet the required values. In this study, the effect of hot extrusion on the Zn-Ag-Mn-Cu-Zr-Ti alloy is characterized. Additionally, thermal treatments at 390 °C for 15, 25, 40, 60, and 120 min were performed to evaluate the effect of intermetallic phase fractions on the corrosion resistance and mechanical strength. Quantitative analysis of X-ray diffraction data demonstrates that the fractions of the MnZn13, ZrZn22, and Zn0.75Ag0.15Mn0.10 intermetallic phases decrease as the thermal treatment time increases. Corrosion tests reveal a reduction in the corrosion rate of the extruded alloy after thermal treatment. The results of uniaxial compression tests and tensile tests show lower strength and higher ductility in all heat-treated conditions compared with the as-extruded condition.
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Superhydrophobic surfaces are attractive as self-cleaning protective coatings in harsh environments with extreme temperatures and pH levels. Hexagonal phase boron nitride (h-BN) films are promising protective coatings due to their extraordinary chemical and thermal stability. However, their high surface energy makes them hydrophilic and thus not applicable as water repelling coatings. Our recent discovery on the superhydrophobicity of boron nitride nanotubes (BNNTs) is thus contradicting with the fact that BN materials would not be hydrophobic. To resolve this contradiction, we have investigated BNNT coatings by time-dependent contact angle measurement, thermogravimetry, IR spectroscopy, and electron microscopy. We found that the wettability of BNNTs is determined by the packing density, orientation, length of nanotubes, and the environmental condition. The origins of superhydrophobicity of these BNNT coatings are identified as (1) surface morphology and (2) hydrocarbon adsorbates on BNNTs. Hydrocarbon molecules adsorb spontaneously on the curved surfaces of nanotubes more intensively than on flat surfaces of BN films. This means the surface energy of BNNTs was enhanced by their large curvatures and thus increased the affinity of BNNTs to adsorb airborne molecules, which in turn would reduce the surface energy of BNNTs and make them hydrophobic. Our study revealed that both high-temperature and UV-ozone treatments can remove these adsorbates and lead to restitution of hydrophilic BN surface. However, nanotubes have a unique capability in building a hydrophobic layer of adsorbates after a few hours of exposure to ambient air.
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Compostos de Boro/química , Nanotubos , Termodinâmica , Microscopia Eletrônica de Varredura , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The metallurgical engineering of bioresorbable zinc (Zn)-based medical alloys would greatly benefit from clarification of the relationships between material properties and biological responses. Here we investigate the biocompatibility of three Zn-based silver (Ag)-containing alloys, ranging from binary to quinary alloy systems. Selected binary and quinary Zn-Ag-based alloys underwent solution treatment (ST) to increase the solubility of Ag-rich phases within the Zn bulk matrix, yielding two different microstructures (one without ST and a different one with ST) with the same elemental composition. This experimental design was intended to clarify the relationship between elemental profile/microstructure and biocompatibility for the Zn-Ag system. We found that the quinary alloy system (Zn-4Ag-0.8Cu-0.6Mn-0.15Zr) performed significantly better, in terms of histomorphometry, than any alloy system we have evaluated to date. Furthermore, when solution treated to increase strength and ductility and reduce the fraction of Ag-rich phases, the quinary alloy's biocompatibility further improved. In vitro corrosion testing and metallographic analysis of in vivo implants demonstrated a more uniform mode of corrosion for the solution treated alloy. We conclude that Zn-Ag alloys can be engineered through alloying to substantially reduce neointimal growth. The positive effect on neointimal growth can be further enhanced by dissolving the AgZn3 precipitates in the Zn matrix to improve the corrosion uniformity. These findings demonstrate that neointimal-forming cells can be regulated by elemental additions and microstructural changes in degradable Zn-based implant materials. STATEMENT OF SIGNIFICANCE: The metallurgical engineering of bioresorbable zinc (Zn)-based medical alloys would greatly benefit from clarification of the relationships between material properties and biological responses. Here, selected binary and quinary Zn-Ag-based alloys underwent solution treatment (ST) to increase the solubility of Ag-rich phases within the Zn bulk matrix, yielding two different microstructures (one without ST and a different one with ST) with the same elemental composition. We found that applying a thermal treatment restores mechanical strength and mitigates the strain rate sensitivity of Zn-Ag alloys by dissolving AgZn3 precipitates. Ag-rich nano-precipitates in Zn decrease biocompatibility, a phenomenon that can be counteracted by dissolving the AgZn3 precipitates in the bulk Zn matrix.
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Ligas , Zinco , Implantes Absorvíveis , Ligas/química , Ligas/farmacologia , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Corrosão , Teste de Materiais , Stents , Zinco/química , Zinco/farmacologiaRESUMO
Zinc is an essential trace element having various structural, catalytic and regulatory interactions with an estimated 3000 proteins. Zinc has drawn recent attention for its use, both as pure metal and alloyed, in arterial stents due to its biodegradability, biocompatibility, and low corrosion rates. Previous studies have demonstrated that zinc metal implants prevent the development of neointimal hyperplasia, which is a common cause of restenosis following coronary intervention. This suppression appears to be smooth muscle cell-specific, as reendothelization of the neointima is not inhibited. To better understand the basis of zinc's differential effects on rat aortic smooth muscle (RASMC) versus endothelial (RAENDO) cells, we conducted a transcriptomic analysis of both cell types following one-week continuous treatment with 5 µM or 50 µM zinc. This analysis indicated that genes whose protein products regulate mitochondrial functions, including oxidative phosphorylation and fusion/fission, are differentially affected by zinc in the two cell types. To better understand this, we performed Seahorse metabolic flux assays and quantitative imaging of mitochondrial networks in both cell types. Zinc treatment differently affected energy metabolism and mitochondrial structure/function in the two cell types. For example, both basal and maximal oxygen consumption rates were increased by zinc in RASMC but not in RAENDO. Zinc treatment increased apparent mitochondrial fusion in RASMC cells but increased mitochondrial fission in RAENDO cells. These results provide some insight into the mechanisms by which zinc treatment differently affects the two cell types and this information is important for understanding the role of zinc treatment in vascular cells and improving its use in biodegradable metal implants.
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The term superhydrophobicity was introduced in 1996 to describe water-repellent fractal surfaces, made of a hydrophobic material, on which water drops remain as almost perfect spheres and roll off such surfaces leaving no residue. Today, superhydrophobic surfaces are defined as textured materials (and coatings) on (nonsmooth) surfaces on which water forms contact angles 150° and larger, with only a few degrees of contact angle hysteresis (or sliding angle). The terms superhydrophilicity and superwetting were introduced a few years after the term superhydrophobicity to describe the complete spreading of water or liquid on substrates. The definition of superhydrophilic and superwetting substrates has not been clarified yet, and unrestricted use of these terms sometimes stirs controversy. This Letter briefly reviews the superwetting phenomenon and offers a suggestion on defining superhydrophilic and superwetting substrates and surfaces.
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Biodegradable arterial implants based on zinc have been found to suppress neointimal hyperplasia, suggesting that biodegradable materials containing zinc may be used to construct vascular implants with a reduced rate of restenosis. However, the molecular mechanism has remained unclear. In this report, we show that zinc-containing materials can be used to prevent neointimal formation when implanted into the rat aorta. Indeed, neointimal cells were significantly more TUNEL positive and alpha-actin negative at the interface of biodegradable zinc vs. biostable platinum implants, in association with greater caspase-3 activity. Although zinc stimulated extensive neointimal smooth muscle cell (SMC) death, macrophage and proinflammatory markers CD68 and iNOS were not increased in neointimal tissue relative to biostable platinum control implants. Using arterial explants, ionic zinc was confirmed to promote SMC apoptosis by activating the caspase apoptotic signaling pathway. These observations suggest that zinc-containing materials can be used to construct vascular implants such as stents with reduced neointimal hyperplasia.
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Implantes Absorvíveis , Músculo Liso Vascular/patologia , Miócitos de Músculo Liso/patologia , Zinco/farmacologia , Animais , Antígenos CD/metabolismo , Antígenos de Diferenciação Mielomonocítica/metabolismo , Caspases/metabolismo , Ativação Enzimática , Hiperplasia , Miócitos de Músculo Liso/efeitos dos fármacos , Neointima/patologia , Óxido Nítrico Sintase Tipo II/metabolismo , RatosRESUMO
Zn-based alloys are recognized as promising bioabsorbable materials for cardiovascular stents, due to their biocompatibility and favorable degradability as compared to Mg. However, both low strength and intrinsic mechanical instability arising from a strong strain rate sensitivity and strain softening behavior make development of Zn alloys challenging for stent applications. In this study, we developed binary Zn-4.0Ag and ternary Zn-4.0Ag-xMn (where x = 0.2-0.6wt%) alloys. An experimental methodology was designed by cold working followed by a thermal treatment on extruded alloys, through which the effects of the grain size and precipitates could be thoroughly investigated. Microstructural observations revealed a significant grain refinement during wire drawing, leading to an ultrafine-grained (UFG) structure with a size of 700 nm and 200 nm for the Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. Mn showed a powerful grain refining effect, as it promoted the dynamic recrystallization. Furthermore, cold working resulted in dynamic precipitation of AgZn3 particles, distributing throughout the Zn matrix. Such precipitates triggered mechanical degradation through an activation of Zn/AgZn3 boundary sliding, reducing the tensile strength by 74% and 57% for Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. The observed precipitation softening caused a strong strain rate sensitivity in cold drawn alloys. Short-time annealing significantly mitigated the mechanical instability by reducing the AgZn3 fraction. The ternary alloy wire showed superior microstructural stability relative to its Mn-free counterpart due to the pinning effect of Mn-rich particles on the grain boundaries. Eventually, a shift of the corrosion regime from localized to more uniform was observed after the heat treatment, mainly due to the dissolution of AgZn3 precipitates. STATEMENT OF SIGNIFICANCE: Owing to its promising biodegradability, zinc has been recognized as a potential biodegradable material for stenting applications. However, Zn's poor strength alongside intrinsic mechanical instability have propelled researchers to search for Zn alloys with improved mechanical properties. Although extensive researches have been conducted to satisfy the mentioned concerns, no Zn-based alloys with stabilized mechanical properties have yet been reported. In this work, the mechanical properties and stability of the Zn-Ag-based alloys were systematically evaluated as a function of microstructural features. We found that the microstructure design in Zn alloys can be used to find an effective strategy to not only improve the strength and suppress the mechanical instability but also to minimize any damage by augmenting the corrosion uniformity.
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Implantes Absorvíveis , Ligas/química , Vasos Sanguíneos/patologia , Stents , Zinco/química , Corrosão , Teste de Materiais , Soluções , Estresse Mecânico , Resistência à Tração , Difração de Raios XRESUMO
Zinc (Zn) has emerged as a promising bioresorbable stent material due to its satisfactory corrosion behavior and excellent biocompatibility. However, for load bearing implant applications, alloying is required to boost its mechanical properties as pure Zn exhibits poor strength. Unfortunately, an increase in inflammation relative to pure Zn is a commonly observed side-effect of Zn alloys. Consequently, the development of a Zn-based alloy that can simultaneously feature improved mechanical properties and suppress inflammatory responses is a big challenge. Here, a bioresorbable, biocompatible Zn-Ag-based quinary alloy was comprehensively evaluated in vivo, in comparison to reference materials. The inflammatory and smooth muscle cellular response was characterized and correlated to metrics of neointimal growth. We found that implantation of the quinary alloy was associated with significantly improved inflammatory activities relative to the reference materials. Additionally, we found that inflammation, but not smooth muscle cell hyperplasia, significantly correlates to neointimal growth for Zn alloys. The results suggest that inflammation is the main driver of neointimal growth for Zn-based alloys and that the quinary Zn-Ag-Mn-Zr-Cu alloy may impart inflammation-resistance properties to arterial implants.