3D printing of polymers is accomplished easily with thermoplastics as the extruded hot melt solidifies rapidly during the printing process. Printing with liquid polymer precursors is more challenging ...due to their longer curing times. One curable liquid polymer of specific interest is polydimethylsiloxane (PDMS). This study demonstrates a new efficient technique for 3D printing with PDMS by using a capillary suspension ink containing PDMS in the form of both precured microbeads and uncured liquid precursor, dispersed in water as continuous medium. The PDMS microbeads are held together in thixotropic granular paste by capillary attraction induced by the liquid precursor. These capillary suspensions possess high storage moduli and yield stresses that are needed for direct ink writing. They could be 3D printed and cured both in air and under water. The resulting PDMS structures are remarkably elastic, flexible, and extensible. As the ink is made of porous, biocompatible silicone that can be printed directly inside aqueous medium, it can be used in 3D printed biomedical products, or in applications such as direct printing of bioscaffolds on live tissue. This study demonstrates a number of examples using the high softness, elasticity, and resilience of these 3D printed structures.
An efficient technique for fabricating multiphase 3D printable polydimethylsiloxane (PDMS) ink is introduced. The ink is a capillary suspension consisting of PDMS microbeads (cured), PDMS liquid precursor (uncured), and water (continuous phase). Upon curing, the printed PDMS ink becomes highly porous, elastic, flexible, and extensible, which promises industrial applications such as biomedical products and bioscaffolds.
Silver nanoparticles have antibacterial properties, but their use has been a cause for concern because they persist in the environment. Here, we show that lignin nanoparticles infused with silver ...ions and coated with a cationic polyelectrolyte layer form a biodegradable and green alternative to silver nanoparticles. The polyelectrolyte layer promotes the adhesion of the particles to bacterial cell membranes and, together with silver ions, can kill a broad spectrum of bacteria, including Escherichia coli, Pseudomonas aeruginosa and quaternary-amine-resistant Ralstonia sp. Ion depletion studies have shown that the bioactivity of these nanoparticles is time-limited because of the desorption of silver ions. High-throughput bioactivity screening did not reveal increased toxicity of the particles when compared to an equivalent mass of metallic silver nanoparticles or silver nitrate solution. Our results demonstrate that the application of green chemistry principles may allow the synthesis of nanoparticles with biodegradable cores that have higher antimicrobial activity and smaller environmental impact than metallic silver nanoparticles.
We developed a method for the fabrication of novel biodegradable nanoparticles (NPs) from lignin which are apparently non‐toxic for microalgae and yeast. We compare two alternative methods for the ...synthesis of lignin NPs which result in particles of very different stability upon change of pH. The first method is based on precipitation of low‐sulfonated lignin from an ethylene glycol solution by using diluted acidic aqueous solutions, which yields lignin NPs that are stable over a wide range of pH. The second approach is based on the acidic precipitation of lignin from a high‐pH aqueous solution which produces NPs stable only at low pH. Our study reveals that lignin NPs from the ethylene glycol‐based precipitation contain densely packed lignin domains which explain the stability of the NPs even at high pH. We characterised the properties of the produced lignin NPs and determined their loading capacities with hydrophilic actives. The results suggest that these NPs are highly porous and consist of smaller lignin domains. Tests with microalgae like Chlamydomonas reinhardtii and yeast incubated in lignin NP dispersions indicated that these NPs lack measurable effect on the viability of these microorganisms. Such biodegradable and environmentally compatible NPs can find applications as drug delivery vehicles, stabilisers of cosmetic and pharmaceutical formulations, or in other areas where they may replace more expensive and potentially toxic nanomaterials.
Let′s go bio: Fabrication of novel biodegradable nanoparticles (NPs) from lignin is reported by two alternative methods which yield particles of different stability upon change of pH (see picture). These lignin NPs have no apparent effect on the viability of microalgae and yeast cells and may find potential applications as drug delivery vehicles and stabilisers of cosmetic and pharmaceutical formulations.
The design of hydrogels where multiple interpenetrating networks enable enhanced mechanical properties can broaden their field of application in biomedical materials, 3D printing, and soft robotics. ...We report a class of self-reinforced homocomposite hydrogels (HHGs) comprised of interpenetrating networks of multiscale hierarchy. A molecular alginate gel is reinforced by a colloidal network of hierarchically branched alginate soft dendritic colloids (SDCs). The reinforcement of the molecular gel with the nanofibrillar SDC network of the same biopolymer results in a remarkable increase of the HHG's mechanical properties. The viscoelastic HHGs show >3× larger storage modulus and >4× larger Young's modulus than either constitutive network at the same concentration. Such synergistically enforced colloidal-molecular HHGs open up numerous opportunities for formulation of biocompatible gels with robust structure-property relationships. Balance of the ratio of their precursors facilitates precise control of the yield stress and rate of self-reinforcement, enabling efficient extrusion 3D printing of HHGs.
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Saponins are natural surfactants which can provide highly viscoelastic interfaces. This property can be used to quantify precisely the effect of interfacial dilatational elasticity on ...the various rheological properties of bulk emulsions.
We measured the interfacial dilatational elasticity of adsorption layers from four saponins (Quillaja, Escin, Berry, Tea) adsorbed on hexadecane-water and sunflower oil-water interfaces. In parallel, the rheological properties under steady and oscillatory shear deformations were measured for bulk emulsions, stabilized by the same saponins (oil volume fraction between 75 and 85%).
Quillaja saponin and Berry saponin formed solid adsorption layers (shells) on the SFO-water interface. As a consequence, the respective emulsions contained non-spherical drops. For the other systems, the interfacial elasticities varied between 2 mN/m and 500 mN/m. We found that this interfacial elasticity has very significant impact on the emulsion shear elasticity, moderate effect on the dynamic yield stress, and no effect on the viscous stress of the respective steadily sheared emulsions. The last conclusion is not trivial, because the dilatational surface viscoelasticity is known to have strong impact on the viscous stress of steadily sheared foams. Mechanistic explanations of all observed effects are described.
Academic and industrial research on nanofibres is an area of increasing global interest, as seen in the continuously multiplying number of research papers and patents and the broadening range of ...chemical, medical, electrical and environmental applications. This in turn expands the size of the market opportunity and is reflected in the significant rise of entrepreneurial activities and investments in the field. Electrospinning is probably the most researched top-down method to form nanofibres from a remarkable range of organic and inorganic materials. It is well known and discussed in many comprehensive studies, so why this review? As we read about yet another "novel" method producing multifunctional nanomaterials in grams or milligrams in the laboratory, there is hardly any research addressing how these methods can be safely, consistently and cost-effectively up-scaled. Despite two decades of governmental and private investment, the productivity of nanofibre forming methods is still struggling to meet the increasing demand. This hinders the further integration of nanofibres into practical large-scale applications and limits current uses to niche-markets. Looking into history, this large gap between supply and demand of synthetic fibres was seen and addressed in conventional textile production a century ago. The remarkable achievement was accomplished via extensive collaborative research between academia and industry, applying ingenious solutions and technological convergence from polymer chemistry, physical chemistry, materials science and engineering disciplines. Looking into the present, current advances in electrospinning and nanofibre production are showing similar interdisciplinary technological convergence, and knowledge of industrial textile processing is being combined with new developments in nanofibre forming methods. Moreover, many important parameters in electrospinning and nanofibre spinning methods overlap parameters extensively studied in industrial fibre processing. Thus, this review combines interdisciplinary knowledge from the academia and industry to facilitate technological convergence and offers insight for upscaling electrospinning and nanofibre production. It will examine advances in electrospinning within a framework of large-scale fibre production as well as alternative nanofibre forming methods, providing a comprehensive comparison of conventional and contemporary fibre forming technologies. This study intends to stimulate interest in addressing the issue of scale-up alongside novel developments and applications in nanofibre research.
Despite the considerable advances of molecular-thermodynamic theory of micelle growth, agreement between theory and experiment has been achieved only in isolated cases. A general theory that can ...provide self-consistent quantitative description of the growth of wormlike micelles in mixed surfactant solutions, including the experimentally observed high peaks in viscosity and aggregation number, is still missing. As a step toward the creation of such theory, here we consider the simplest system – nonionic wormlike surfactant micelles from polyoxyethylene alkyl ethers, CiEj. Our goal is to construct a molecular-thermodynamic model that is in agreement with the available experimental data. For this goal, we systematized data for the micelle mean mass aggregation number, from which the micelle growth parameter was determined at various temperatures. None of the available models can give a quantitative description of these data. We constructed a new model, which is based on theoretical expressions for the interfacial-tension, headgroup-steric and chain-conformation components of micelle free energy, along with appropriate expressions for the parameters of the model, including their temperature and curvature dependencies. Special attention was paid to the surfactant chain-conformation free energy, for which a new more general formula was derived. As a result, relatively simple theoretical expressions are obtained. All parameters that enter these expressions are known, which facilitates the theoretical modeling of micelle growth for various nonionic surfactants in excellent agreement with the experiment. The constructed model can serve as a basis that can be further upgraded to obtain quantitative description of micelle growth in more complicated systems, including binary and ternary mixtures of nonionic, ionic and zwitterionic surfactants, which determines the viscosity and stability of various formulations in personal-care and house-hold detergency.
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•Preceding works on growth of wormlike micelles in surfactant solutions are reviewed.•Data for micelle aggregation number vs. surfactant concentration are systematized.•Quantitative model of growth of nonionic wormlike surfactant micelles is proposed.•Formula for the free energy of chain conformations inside the micelle is derived.•The concentration and temperature dependencies of aggregation number are described.
Surface active biopolymers such as proteins can form films with particularly high interfacial elasticities and viscosities and these molecules are widely exploited as foaming and emulsifying agents ...in foods. Solid particles of the correct size and wetting characteristics can also be extremely effective stabilizers of foams and emulsions, although the underlying mechanism of stabilization is somewhat different. Relatively little is known about what happens when both surface active polymers and surface active particles are present together. This work presents recent findings on the effects of mixtures of proteins plus novel food-compatible surface active particles. The proteins include caseins and whey proteins. The surface active particles prepared include cellulose
+
ethyl cellulose complexes, hydrophobically-modified starch granule particles and stable (non-spreading) protein-stabilized oil droplets. Interfacial shear rheology of adsorbed films was measured via a biconical bob apparatus and interfacial dilatational rheology was measured via a Langmuir trough type apparatus. The corresponding stability of bubbles to coalescence and disproportionation was assessed in separate experiments. Stability of oil-in-water emulsions was assessed via measurement of particle size distributions as function of time and visual assessment of the tendency to creaming and oiling off. In general, it is shown that the surface active particles on their own exhibit much lower measures of interfacial elasticity and viscosity than the proteins, but in combination with the proteins they appear to enhance the interfacial viscoelasticity considerably, with concomitant increases in bubble and emulsion droplet stability. There is little evidence of attractive interactions between the particles and the proteins, so a possible explanation of the increased stability is that the proteins increase the accumulation of particles at the interface, giving rise to increased jamming of particles at the interface.
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The interplay between morphology, excluded volume and adhesivity of particles critically determines the physical properties of numerous soft materials and coatings
. Branched particles
or nanofibres
..., nanofibrillated cellulose
or fumed silica
can enhance the structure-building abilities of colloids, whose adhesion may also be increased by capillarity or binding agents
. Nonetheless, alternative mechanisms of strong adhesion found in nature involve fibrillar mats with numerous subcontacts (contact splitting)
as seen in the feet of gecko lizards and spider webs
. Here, we describe the fabrication of hierarchically structured polymeric microparticles having branched nanofibre coronas with a dendritic morphology. Polymer precipitation in highly turbulent flow results in microparticles with fractal branching and nanofibrillar contact splitting that exhibit gelation at very low volume fractions, strong interparticle adhesion and binding into coatings and non-woven sheets. These soft dendritic particles also have potential advantages for food, personal care or pharmaceutical product formulations.
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