Understanding the generation and evolution of hydrophobicity of silane modified fly ash/slag based geopolymers

Silanes are widely used to enhance the corrosion resistance of cement-based materials by endowing the substrate with hydrophobicity. However, their applications in fly ash/slag based geopolymer (FSBG) are still rare. This study comprehensively investigates the hydrophobicity properties and reaction products of FSBG modified by isooctyltriethoxysilane admixture to reveal the mechanisms involved in the generation and evolution of hydrophobization effect. In spite of the verified compromise in compressive strength of modified FSBG for longer ages, the early strength at 1 day is amazingly found to slightly increase, ascribed to the heat release along with the hydrolysis of silane. The reduction of porosity is caused by the siloxane products of silane after condensation reactions and thus does not show consistencies to the decreasing compressive strength as well as the formation of hydration products. The amount of N-A-S-H gel is found to reduce more intensively compared to the C-A-S-H gel when silane is used. The evolution of contact angle on the surface of modified FSBG is dependent on the mutual effect of superficial density of silane and porosity, with the former controlled by the amount of coupling sites. The formula of contact angle evolution is proposed and can be potentially used to regulate and govern the hydrophobicity properties of FSBG, with the feasibility to be applied in other geopolymers and cement-based materials.</p

Nanoporous monolithic microsphere arrays have anti-adhesive properties independent of humidity

Bioinspired artificial surfaces with tailored adhesive properties have attracted significant interest. While fibrillar adhesive pads mimicking gecko feet are optimized for strong reversible adhesion, monolithic microsphere arrays mimicking the slippery zone of the pitchers of carnivorous plants of the genus Nepenthes show anti-adhesive properties even against tacky counterpart surfaces. In contrast to the influence of topography, the influence of relative humidity (RH) on adhesion has been widely neglected. Some previous works deal with the influence of RH on the adhesive performance of fibrillar adhesive pads. Commonly, humidity-induced softening of the fibrils enhances adhesion. However, little is known on the influence of RH on solid anti-adhesive surfaces. We prepared polymeric nanoporous monolithic microsphere arrays (NMMAs) with microsphere diameters of a few 10 {\mu}m to test their anti-adhesive properties at RHs of 2 % and 90 %. Despite the presence of continuous nanopore systems through which the inner nanopore walls were accessible to humid air, the topography-induced anti-adhesive properties of NMMAs on tacky counterpart surfaces were retained even at RH = 90 %. This RH-independent robustness of the anti-adhesive properties of NMMAs significantly contrasts the adhesion enhancement by humidity-induced softening on nanoporous fibrillar adhesive pads made of the same material

Advanced SERS sensor based on capillarity-assisted preconcentration through gold nanoparticles-decorated porous nanorods

A preconcentrating surface-enhanced Raman scattering (SERS) sensor for the analysis of liquid-soaked tissue, tiny liquid droplets and thin liquid films without the necessity to collect the analyte is reported. The SERS sensor is based on a blockcopolymer membrane containing a spongy-continuous pore system. The sensor's upper side is an array of porous nanorods having tips functionalized with Au nanoparticles. Capillarity in combination with directional evaporation drives the analyte solution in contact with the flat yet nanoporous underside of the SERS sensor through the continuous nanopore system toward the nanorod tips where non-volatile components of the analyte solution precipitate at the Au nanoparticles. The nanorod architecture increases the sensor surface in the detection volume and facilitates analyte preconcentration driven by directional solvent evaporation. The model analyte 5,5'-dithiobis(2-nitrobenzoic acid) can be detected in a 1 x 10-3 m solution about 300 ms after the sensor is brought into contact with the solution. Moreover, a sensitivity of 0.1 ppm for the detection of the dissolved model analyte is achieved

Hybrid Surface Patterns Mimicking the Design of the Adhesive Toe Pad of Tree Frog

Biological materials achieve directional reinforcement with oriented assemblies of anisotropic building blocks. One such example is the nanocomposite structure of keratinized epithelium on the toe pad of tree frogs, in which hexagonal arrays of (soft) epithelial cells are crossed by densely packed and oriented (hard) keratin nanofibrils. Here, a method is established to fabricate arrays of tree-frog-inspired composite micropatterns composed of polydimethylsiloxane (PDMS) micropillars embedded with polystyrene (PS) nanopillars. Adhesive and frictional studies of these synthetic materials reveal a benefit of the hierarchical and anisotropic design for both adhesion and friction, in particular, at high matrix-fiber interfacial strengths. The presence of PS nanopillars alters the stress distribution at the contact interface of micropillars and therefore enhances the adhesion and friction of the composite micropattern. The results suggest a design principle for bioinspired structural adhesives, especially for wet environments

Effective Elastic Modulus of Structured Adhesives: From Biology to Biomimetics

Micro- and nano-hierarchical structures (lamellae, setae, branches, and spatulae) on the toe pads of many animals play key roles for generating strong but reversible adhesion for locomotion. The hierarchical structure possesses significantly reduced, effective elastic modulus (Eeff), as compared to the inherent elastic modulus (Einh) of the corresponding biological material (and therefore contributes to a better compliance with the counterpart surface). Learning from nature, three types of hierarchical structures (namely self-similar pillar structure, lamella–pillar hybrid structure, and porous structure) have been developed and investigated

Guiding cell migration with microscale stiffness patterns and undulated surfaces

By placing stiff structures under soft materials, prior studies have demonstrated that cells sense and prefer to position themselves over the stiff structures. However, an understanding of how cells migrate on such surfaces has not been established. Many studies have also shown that cells readily align to surface topography. Here we investigate the influence of these two aspects in directing cell migration on surfaces with 5 and 10 μm line stiffness patterns (a cellular to subcellular length scale). A simple approach to create flat, stiffness-patterned surfaces by suspending a thin, low modulus polydimethylsiloxane (PDMS) film over a high modulus PDMS structure is presented, as well as a route to add undulations. We confirm that cells are able to sense through the thin film by observation of focal adhesions being positioned on stiff regions. We examine migration by introducing migration efficiency, a quantitative parameter to determine how strongly cells migrate in a certain direction. We found that cells have a preference to align and migrate along stiffness patterns while the addition of undulations boosts this effect, significantly increasing migration efficiency in either case. Interestingly, we found speed to play little role in the migration efficiency and to be mainly influenced by the top layer modulus. Our results demonstrate that both stiffness patterns and surface undulations are important considerations when investigating the interactions of cells with biomaterial surfaces. Statement of Significance Two common physical considerations for cell-surface interactions include patterned stiffness and patterned topography. However, their relative influences on cell migration behavior have not been established, particularly on cellular to subcellular scale patterns. For stiffness patterning, it has been recently shown that cells tend to position themselves over a stiff structure that is placed under a thin soft layer. By quantifying the directional migration efficiency on such surfaces with and without undulations, we show that migration can be manipulated by flat stiffness patterns, although surface undulations also play a strong role. Our results offer insight on the effect of cellular scale stiffness and topographical patterns on cell migration, which is critical for the development of fundamental cell studies and engineered implants.Fil: Pham, Jonathan T.. Max Planck Institute for Polymer Research; AlemaniaFil: Xue, Longjian. Max Planck Institute for Polymer Research; AlemaniaFil: del Campo, Aránzazu. Leibniz Institute for New Materials; Alemania. Universitat Saarland; AlemaniaFil: Salierno, Marcelo Javier. Max Planck Institute for Polymer Research; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentin