Martti Toivakka

Nanostructures increase water droplet adhesion on hierarchically rough superhydrophobic surfaces.

Hierarchical roughness is known to effectively reduce the liquid-solid contact area and water droplet adhesion on superhydrophobic surfaces, which can be seen for example in the combination of submicrometer and micrometer scale structures on the lotus leaf. The submicrometer scale fine structures, which are often referred to as nanostructures in the literature, have an important role in the phenomenon of superhydrophobicity and low water droplet adhesion. Although the fine structures are generally termed as nanostructures, their actual dimensions are often at the submicrometer scale of hundreds of nanometers. Here we demonstrate that small nanometric structures can have very different effect on surface wetting compared to the large submicrometer scale structures. Hierarchically rough superhydrophobic TiO(2) nanoparticle surfaces generated by the liquid flame spray (LFS) on board and paper substrates revealed that the nanoscale surface structures have the opposite effect on the droplet adhesion compared to the larger submicrometer and micrometer scale structures. Variation in the hierarchical structure of the nanoparticle surfaces contributed to varying droplet adhesion between the high- and low-adhesive superhydrophobic states. Nanoscale structures did not contribute to superhydrophobicity, and there was no evidence of the formation of the liquid-solid-air composite interface around the nanostructures. Therefore, larger submicrometer and micrometer scale structures were needed to decrease the liquid-solid contact area and to cause the superhydrophobicity. Our study suggests that a drastic wetting transition occurs on superhydrophobic surfaces at the nanometre scale; i.e., the transition between the Cassie-Baxter and Wenzel wetting states will occur as the liquid-solid-air composite interface collapses around nanoscale structures. Consequently, water adheres tightly to the surface by penetrating into the nanostructure. The droplet adhesion mechanism presented in this paper gives valuable insight into a phenomenon of simultaneous superhydrophobicity and high water droplet adhesion and contributes to a more detailed comprehension of superhydrophobicity overall.

Paper-based microfluidics: fabrication technique and dynamics of capillary-driven surface flow.

Paper-based devices provide an alternative technology for simple, low-cost, portable, and disposable diagnostic tools for many applications, including clinical diagnosis, food quality control, and environmental monitoring. In this study we report a two-step fabrication process for creating two-dimensional microfluidic channels to move liquids on a hydrophobized paper surface. A highly hydrophobic surface was created on paper by TiO2 nanoparticle coating using a high-speed, roll-to-roll liquid flame spray technique. The hydrophilic pattern was then generated by UV irradiation through a photomask utilizing the photocatalytic property of TiO2. The flow dynamics of five model liquids with differing surface tensions 48-72 mN·m(-1) and viscosities 1-15 mN·m(-2) was studied. The results show that the liquid front (l) in a channel advances in time (t) according to the power law l=Zt0.5 (Z is an empirical constant which depend on the liquid properties and channel dimensions). The flow dynamics of the liquids with low viscosity show a dependence on the channel width and the droplet volume, while the flow of liquids with high viscosity is mainly controlled by the viscous forces.

Nanoparticle Deposition from Liquid Flame Spray onto Moving Roll-to-Roll Paperboard Material

Nanostructured coatings have been prepared on a flexible, moving paperboard using deposition of ca. 40-nm-sized titanium dioxide nanoparticles generated by a liquid flame spray process, directly above the paperboard, to achieve improved functional properties for the material. Properties such as surface wettability can be extensively improved by a thin layer of nanoparticles on the substrate. Owing to the vulnerability to heat, the substrate needs to be moved rapidly through the flame. This, on the other hand, generates a setting for a roll-to-roll coating process, which favors upscaling of the method. In this article, we characterize the flame process for nanoparticle coating and quantify the operational window for this method. The amount of deposited material as a function of substrate speed through the flame is discussed. Although the thermophoretic flux of nanoparticles is estimated to be very high from the hot flame onto the cold substrate, other factors were observed to limit the deposited amount of particles. Total mass yields of 5%–20% of the injected precursor material into the titanium dioxide nanocoating on the paperboard were achieved. With these yields, a highly hydrophobic surface was obtained by a mass loading of 10–50 mg/m2 of titanium dioxide on the paperboard.

ToF-SIMS analysis of UV-switchable TiO2-nanoparticle-coated paper surface.

The chemical composition of a TiO2 nanoparticle coated paper surface was analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) to study the interconnection between wettability and surface chemistry on the nanoscale. In this work, a superhydrophobic TiO2 surface rich in carboxyl-terminated molecules was created by a liquid flame spray process. The TiO2 nanoparticle coated paper surface can be converted by photocatalytic oxidation into a highly hydrophilic one. Interestingly, the hydrophilic surface can be converted back into a superhydrophobic surface by heat treatment. The results showed that both ultraviolet A (UVA) and oven treatment induce changes in the surface chemistry within a few nanometers of the paper surface. These findings are consistent with those from our previously reported X-ray photoelectron spectroscopy (XPS) analysis, but the ToF-SIMS analysis yields more accurate insight into the surface chemistry.

Rheology of cellulose nanofibers suspensions: Boundary driven flow

Cellulose nanofibers (CNFs) are an exciting new renewable material produced from wood fibers. Even at low solids content, CNF-water suspensions have a complex rheology that includes extreme shear-thinning as well as viscoelastic properties and a yield stress similar to other suspensions of nanoscale particles. When characterizing the rheology of CNF suspensions, the measurement method may influence the results due to a water layer expected at the boundary, but it is unclear how the behavior near walls influences the measurement method. Parallel-plate, Couette, and vane geometries were used to compare yielding and flow of CNF suspensions obtained by steady-state shear and oscillatory rheological measurements. Five different techniques were compared as methods to obtain a yield stress. Cone and plate geometries were found to lead to sample ejection at low shear rates: Floc-floc interactions can explain this ejection. The suspensions violated the Cox-Merz rule by a significant amount; this behavior has been explained in the past as weak gel structures that break down in shear, but for this material it seems that the acting mechanism involves the formation of a water-rich layer near the solid boundaries in steady shear, while for oscillatory tests, these layers do not form. For suspensions lower than 3% solids, the yield stress measured by different procedures was within 20% of each other, but for high solids suspensions, differences between the methods could be as large as 100%; the water-rich layer formation likely is the cause of these results. Oscillatory methods are suggested as a method to obtain yield stress values for this type of material. The Couette geometry data were below the power-law lines fitted to the parallel-plate geometry data from steady-shear measurements perhaps again attributable to different water-rich layers that form in these different geometries.

Wettability conversion on the liquid flame spray generated superhydrophobic TiO 2 nanoparticle coating on paper and board by photocatalytic decomposition of spontaneously accumulated carbonaceous overlayer

Titanium dioxide (TiO2) is a photoactive material with various interesting and useful properties. One of those is the perfect wettability of TiO2 surface after ultraviolet (UV) illumination. Wettability of a solid surface plays an important role in the field of printing, coating, and adhesion among others. Here we report on a superhydrophobic and photoactive liquid flame spray (LFS) generated TiO2 nanoparticle coating that can be applied on web-like materials such as paper and board in one-step roll-to-roll process. The LFS TiO2 nanoparticle coated paper and board were superhydrophobic instantly after the coating procedure because of spontaneously accumulated carbonaceous overlayer on TiO2, and thus there was no need for any type of separate hydrophobization treatment. The highly photoactive LFS TiO2 nanoparticle coating could be converted steplessly from superhydrophobic to superhydrophilic by UV-illumination, and the coating gave strong response to natural daylight illumination even in the shade. The superhydrophobic LFS TiO2 coated surface can be used as an intelligent substrate, where photo-generated hydrophilic patterns guide the fluid setting and figure formation. Our study reveals that the wettability changes on the LFS TiO2 surface were primarily caused by the photocatalytic removal of the carbonaceous material from TiO2 during the UV-illumination and spontaneous accumulation of the carbonaceous material on the surface of the metal oxide during storage in the dark. The latter mechanism was found to be a temperature activated process which could be significantly speeded up by heat treatment. If other mechanisms such as surface oxidization, increment of hydroxyl groups, or charge separation played a role in the wetting phenomena on TiO2, their effect was rather secondary as the removal and accumulation of the carbonaceous material dominated the wettability changes on the surface. Our study gives valuable information on the complex issue of photo-induced wettability changes on TiO2.

Temperature effects on dynamic water absorption into paper.

Mechanisms controlling short time water absorption and the effect of temperature on water absorption into paper were investigated by analyzing previously published data. A dynamic contact angle effect caused by contact line friction explained the liquid uptake dynamics at short times. The water absorption rate increase with temperature is suggested to be controlled by the molecular processes occurring in front of the advancing liquid front. The increase in the non-equilibrium vapor pressure at air-liquid interface leads to higher water molecule adsorption onto fibers and associated lowering of the solid-gas interfacial tension, thereby increasing the wetting velocity and water absorption. The classical Lucas-Washburn equation was found to be inadequate for predicting water absorption into paper both at short times and as a function of temperature.

Prediction of suspension viscoelasticity through particle motion modeling

Abstract A modified Stokesian dynamics technique is used in an oscillatory shear fleld to obtain the elastic and storage modulus of the suspension of spherical particles in a Newtonian liquid. Electrostatic or steric repulsive forces between suspended particles result in a viscoelastic behavior of a concentrated suspension. The mechanism for energy storage is a particle microstructure phenomenon: the compression of the electrostatic potential by hydrodynamic forces stores energy.

Impact of humidity on functionality of?on-paper printed electronics

A multilayer coated paper substrate, combining barrier and printability properties was manufactured utilizing a pilot-scale slide curtain coating technique. The coating structure consists of a thin mineral pigment layer coated on top of a barrier layer. The surface properties, i.e. smoothness and surface porosity, were adjusted by the choice of calendering parameters. The influence of surface properties on the fine line printability and conductivity of inkjet-printed silver lines was studied. Surface roughness played a significant role when printing narrow lines, increasing the risk of defects and discontinuities, whereas for wider lines the influence of surface roughness was less critical. A smooth, calendered surface resulted in finer line definition, i.e. less edge raggedness. Dimensional stability and its influence on substrate surface properties as well as on the functionality of conductive tracks and transistors were studied by exposure to high/low humidity cycles. The barrier layer of the multilayer coated paper reduced the dimensional changes and surface roughness increase caused by humidity and helped maintain the conductivity of the printed tracks. Functionality of a printed transistor during a short, one hour humidity cycle was maintained, but a longer exposure to humidity destroyed the non-encapsulated transistor.

Measuring solvent barrier properties of paper

New methods for measuring barrier properties against solvents, acids and bases on dispersion coated paper were developed and investigated. Usability, reliability and repeatability were compared both between the new methods and with the standardized method for measuring barrier properties against water vapor. Barrier properties could be measured with all methods and the results obtained by the different methods were in correlation with each other. A qualitative method based on a trace color provided an indicative result, whereas further developed methods also took into account the durability. The effective barrier lifetime could be measured by measuring the conductivity through the substrate as a function of time, or by utilizing a glass prism where the change in refractive index caused by penetrated liquid was monitored, also as a function of time. Barrier properties against water and humidity were also measured and were found not to be predictors for barrier properties against either solvents, or acids or bases, which supports the need to develop new methods.