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Integration of solvothermal reaction products into complex thin-layer architectures is frequently achieved by combinations of layer transfer and subtractive lithography, whereas direct additive substrate patterning with solvothermal reaction products has remained challenging. We report reactive additive capillary stamping under solvothermal conditions as a parallel contact-lithographic access to patterns of solvothermal reaction products in thin-layer configurations. To this end, corresponding precursor inks are infiltrated into mechanically robust mesoporous aerogel stamps derived from double-network hydrogels (DNHGs). The stamp is then brought into contact with a substrate to be patterned under solvothermal reaction conditions inside an autoclave. The precursor ink forms liquid bridges between the topographic surface pattern of the stamp and the substrate. Evaporation-driven enrichment of the precursors in these liquid bridges along with their liquid-bridge-guided conversion into the solvothermal reaction products yields large-area submicron patterns of the solvothermal reaction products replicating the stamp topography. As example, we prepared thin hybrid films, which contained ordered monolayers of superparamagnetic submicron nickel ferrite dots prepared by solvothermal capillary stamping surrounded by nickel electrodeposited in a second, orthogonal substrate functionalization step. The submicron nickel ferrite dots acted as magnetic hardener halving the remanence of the ferromagnetic nickel layer. In this way, thin-layer electromechanical systems, transformers and positioning systems may be customized.

We comparatively analyzed imbibition of polystyrene (PS) into two complementary pore models having pore diameters of about 380 nm and hydroxyl-terminated inorganic-oxidic pore walls, controlled porous glass (CPG) and self-ordered porous alumina (AAO), by X-ray computed tomography and EDX spectroscopy. CPG contains continuous spongy-tortuous pore systems. AAO containing arrays of isolated straight cylindrical pores is a reference pore model with a tortuosity close to 1. Comparative evaluation of the spatiotemporal imbibition front evolution yields important information on the pore morphology of a probed tortuous matrix like CPG and on the imbibition mechanism. To this end, pixel brightness dispersions in tomographic 3D reconstructions and 2D EDX maps of infiltrated AAO and CPG samples were condensed into 1D brightness dispersion profiles normal to the membrane surfaces. Their statistical analysis yielded positions and widths of the imbibition fronts without segmentation or determination of pore positions. The retardation of the imbibition front movement with respect to AAO reference samples may be used as a descriptor for the tortuosity of a tested porous matrix. The velocity of the imbibition front movements in CPG equaled two-thirds of the velocity of the imbibition front movements in AAO. Moreover, the dynamics of the imbibition front broadening discloses whether porous matrices are dominated by cylindrical neck-like pore segments or by nodes. Independent single-meniscus movements in cylindrical AAO pores result in faster imbibition front broadening than in CPG, in which a morphology dominated by nodes results in slower cooperative imbibition front movements involving several menisci.

The properties of porous glasses and their field of application strongly depend on the characteristics of the void space. Understanding the relationship between their porous structure and failure behaviour can contribute to the development of porous glasses with long-term reliability optimized for specific applications. In the present work, we used X-ray computed tomography with nanometric resolution (nano-CT) to image a controlled pore glass (CPG) with 400 nm-sized pores whilst undergoing uniaxial compression in-situ to emulate a stress process. Our results show that in-situ nano-CT provides an ideal platform for identifying the mechanisms of damage within glass with pores of 400 nm, as it allowed the tracking of the pores and struts change of shape during compression until specimen failure. We have also applied computational tools to quantify the microstructural changes within the CPG sample by mapping the displacements and strain fields, and to numerically simulate the behaviour of the CPG using a Fast Fourier Transform/phase-field method. Both experimental and numerical data show local shear deformation, organized along bands, consistent with the appearance and propagation of +/- 45 degrees cracks., Comment: 14 pages, 6 figures

Patterned substrates for optics, electronics, sensing, lab-on-chip technologies, bioanalytics, clinical diagnostics as well as translational and personalized medicine are typically prepared by additive substrate manufacturing including ballistic printing and microcontact printing. However, ballistic printing (e.g., ink jet and aerosol jet printing, laser-induced forward transfer) involves serial pixel-by-pixel ink deposition. Parallel additive pattering by microcontact printing is performed with solid elastomeric stamps suffering from ink depletion after a few stamp-substrate contacts. The throughput limitations of additive state-of-the-art patterning thus arising may be overcome by capillary stamping - parallel additive substrate patterning without ink depletion by mesoporous silica stamps, which enable ink supply through the mesopores anytime during stamping. Thus, either arrays of substrate-bound nanoparticles or colloidal nanodispersions of detached nanoparticles are accessible. We processed three types of model inks: 1) drug solutions, 2) solutions containing metallopolymers and block copolymers as well as 3) nanodiamond suspensions representing colloidal nanoparticle inks. Thus, we obtained aqueous colloidal nanodispersions of stamped drug nanoparticles, regularly arranged ceramic nanoparticles by post-stamping pyrolysis of stamped metallopolymeric precursor nanoparticles and regularly arranged nanodiamond nanoaggregates. Capillary stamping may overcome the throughput limitations of state-of-the-art additive substrate manufacturing while a broad range of different inks can be processed.

Classical microcontact printing involves transfer of molecules adsorbed on the outer surfaces of solid stamps to substrates to be patterned. We prepared spongy mesoporous silica stamps that can be soaked with ink and that were topographically patterned with arrays of submicron contact elements. Multiple successive stamping steps can be carried out under ambient conditions without ink refilling. Lattices of fullerene nanoparticles with diameters in the 100 nm range were obtained by stamping C60/toluene solutions on perfluorinated glass slides partially wetted by toluene. Stamping an ethanolic 1-dodecanethiol solution onto gold-coated glass slides yielded arrays of submicron dots of adsorbed 1-dodecantethiol molecules, even though macroscopic ethanol drops spread on gold. This outcome may be related to the pressure drop across the concave ink menisci at the mesopore openings on the stamp surface counteracting the van der Waals forces between ink and gold surface and/or to reduced wettability of the 1-dodecanethiol dots themselves by ethanol. The chemical surface heterogeneity of gold-coated glass slides functionalized with submicron 1-dodecanethiol dots was evidenced by dewetting of molten polystyrene films eventually yielding ordered arrays of polystyrene nanoparticles

We designed spongy monoliths allowing liquid delivery to their surfaces through continuous nanopore systems (mean pore diameter ca. 40 nm). These nanoporous monoliths were flat or patterned with microspherical structures a few 10 microns in diameter, and their surfaces consisted of aprotic polymer or of TiO2 coatings. Liquid may reduce adhesion forces FAd; possible reasons include screening of solid-solid interactions and poroelastic effects. Softening-induced deformation of flat polymeric monoliths upon contact formation in the presence of liquids enhanced the work of separation WSe. On flat TiO2-coated monoliths, WSe was under wet conditions smaller than under dry conditions, possibly because of liquid-induced screening of solid-solid interactions. Under dry conditions, WSe is larger on flat TiO2-coated monoliths than on flat monoliths with polymeric surface. However, under wet conditions liquid-induced softening results in larger WSe on flat monoliths with polymeric surface than on flat monoliths with oxidic surface. Monolithic microsphere arrays show anti-adhesive properties; FAd and WSe are reduced by at least one order of magnitude as compared to flat nanoporous counterparts. On nanoporous monolithic microsphere arrays, capillarity (WSe is larger under wet than under dry conditions) and solid-solid interactions (WSe is larger on oxide than on polymer) dominate contact mechanics. Thus, the microsphere topography reduces the impact of softening-induced surface deformation and screening of solid-solid interactions associated with liquid supply. Overall, simple modifications of surface topography and chemistry combined with delivery of liquid to the contact interface allow adjusting WSe and FAd over at least one order of magnitude. (...)