Aerogel objects inspired by plant cell wall components and structures were fabricated using extrusion-based 3D printing at cryogenic temperatures. The printing process combines 3D printing with the alignment of rod-shaped nanoparticles through the freeze-casting of aqueous inks. We have named this method direct cryo writing (DCW) as it encompasses in a single processing step traditional directional freeze casting and the spatial fidelity of 3D printing. DCW is demonstrated with inks that are composed of an aqueous mixture of cellulose nanocrystals (CNCs) and xyloglucan (XG), which are the major building blocks of plant cell walls. Rapid fixation of the inks is achieved through tailored rheological properties and controlled directional freezing. Morphological evaluation revealed the role of ice crystal growth in the alignment of CNCs and XG. The structure of the aerogels changed from organized and tubular to disordered and flakey pores with an increase in XG content. The internal structure of the printed objects mimics the structure of various wood species and can therefore be used to create wood-like structures via additive manufacturing technologies using only renewable wood-based materials.

Directed-assembly by standing surface acoustic waves (SSAWs) only requires an acoustic contrast between particles and their surrounding medium. It is therefore highly attractive as this requirement is fulfilled by almost all dispersed systems. Previous studies utilizing SSAWs demonstrated mainly reversible microstructure arrangements from nanoparticles. The surface chemistry of colloids dramatically influences their tendency to aggregate and sinter; therefore, it should be possible to form permanent microstructures with intimate contact between nanoparticles by controlling this property. Dispersed silver nanoparticles in a microfluidic channel were exposed to SSAWs and reversibly accumulated at the pressure nodes. We show that addition of chloride ions that remove the polyacrylic capping of the nanoparticles trigger their sintering and the formation of stable conducting silver microstructures. Moreover, if the destabilizing ions are added prior to nanoparticle assembly while continuously streaming the dispersion through the acoustic aperture, the induced aggregation leads to formation of significantly thinner microstructures, which are (for the first time) unlimited in length by the acoustic apparatus. This new approach overcomes the discrepancy between the need for organic dispersants to prevent unwanted aggregation in the dispersion, and the end product's requirement for intimate contact between the colloidal particles.

Renewable energy technol. and effective energy management are the most crucial factors to consider in the progress toward worldwide energy sustainability. Smart window technol. has a huge potential in energy management as it assists in reducing energy consumption of indoor lighting and air-conditioning in buildings. Electrochromic (EC) materials, which can elec. modulate the transmittance of solar radiation, are one of the most studied smart window materials. In this work, highly transparent SnO2 inverse opal (IO) is used as the framework to electrochem. deposit amorphous WO3 layer to fabricate hybrid SnO2-WO3 core-shell IO structure. The hybrid structure is capable of effective near IR (NIR) modulation while maintaining high visible light transparency in the colored and bleached states. By varying the initial diameter of the polystyrene (PS) opal template and the WO3 electrodeposition time, optimal results can be obtained with the smallest PS diameter of 392 nm and 180 s WO3 electrodeposition. In its colored state, the 392-SnO2-WO3-180 core-shell IO structure shows ≈70% visible light transparency, 62% NIR blockage at 1200 nm, and ≈15% drop in NIR blocking stability after 300 cycles. The SnO2-WO3 core-shell IO structure in this study is a promising EC material for advanced smart window technol.

Two kinds of carbon-based nanozymes were constructed from the same precursor of zeolitic imidazolate framework-8 (ZIF-8) for O2•- determination Hollow carbon cubic nanomaterial (labeled as HCC) was obtained by chem. etching ZIF-8 with tannic acid and a subsequent calcination. A porous carbon cubic nanomaterial (labeled as PCC) was prepared by directly pyrolysis. Then HCC and PCC were immobilized on the surface of screen printed carbon electrodes (SPCE), fabricating HCC and PCC modified electrodes (denoted as HCC/SPCE and PCC/SPCE). HCC/SPCE, best operated at -0.5 V (vs. Ag/AgCl), has a sensitivity of 6.55 × 102 nA μM-1 cm-2 with a detection limit of 207 nM (at S/N = 3) for O2•- sensing. And PCC/SPCE, best operated at -0.4 V (vs. Ag/AgCl), exhibited a superior performance for O2•- detection with a sensitivity of 1.14 × 103 nA μM-1 cm-2 and a low detection limit of 140 nM (at S/N = 3). The two sensors possess excellent reproducibility and stability. They were used to sense O2•- released from HeLa cells. [Figure not available: see fulltext.]

In recent years, there has been significant advancement in smart window technologies due to their effectiveness in reducing energy consumption of indoor lighting and air-conditioning in buildings. Electrochromic (EC) materials, in particular, have been widely studied as they provide a simple method for tuning or modulating visible light and IR (IR) transmittance. In this work, a novel hybrid, multi-layered SnO2-TiO2-WO3 inverse opal (IO) nanostructure has been fabricated via dip-coating and electrodeposition process. This hybrid nanostructure allows an electrochromic smart window for effective near IR (NIR) modulation, with high visible transparency and durable EC cycling stability. The visible transparency of as-fabricated hybrid multi-layered SnO2-TiO2-WO3 IO was measured to be in the range of 67.2-88.0% in the bleached state and 67.0-74.4% in the colored state, resp. Furthermore, the hybrid nanostructure is also able to modulate up to 63.6% NIR radiation at the wavelength of 1200 nm and maintain approx. 82.6% of its NIR blockage capability after 750 reversible cycles. The hybrid multi-layered SnO2-TiO2-WO3 IO nanostructure in this study can potentially be an effective and stable EC material for advanced smart window technol.

Effective management of heat transfer, such as conduction and radiation, through glass windows is one of the most challenging issues in smart window technology. In this work, reduced Graphene Oxide (rGO) thin films of varying thicknesses are fabricated onto Fluorine-doped Tin Oxide (FTO) glass via electrophoretic deposition technique. The sample thicknesses increase with increasing number of deposition cycles (5, 10, 20 cycles). It is hypothesized that such rGO thin films, which are well-known for their high thermal conductivities, can conduct heat away laterally towards heat sinks and reduce near-infrared (NIR) transmittance through them, thus effectively slowing down the temperature increment indoors. The performance of rGO/FTO in reducing indoor temperatures is investigated with a solar simulator and a UV-Vis-NIR spectrophotometer. The 20-cycles rGO thin films showed 30% more NIR blocked at 1000 nm as compared to clean FTO, as well as the least temperature increment of 0.57 °C following 30 min of solar irradiation. Furthermore, the visible transmittance of the as-fabricated rGO films remain on par with commercial solar films, enabling up to 60% of visible light transmittance for optimal balance of transparency and heat reduction. These results suggest that the rGO thin films have great potential in blocking heat transfer and are highly recommended for smart window applications.

Fabrication of dense ceramic objects by 3D printing processes is important in achieving improved functions in many applications, such as mechanical, optical, and electrical devices. It is a challenging process, mainly due to the high content of organic binders within the printed object. Upon heating and sintering, the printed object shrinks and becomes porous due to the decomposition of the organic binder. Herein, a new approach is presented based on the utilization of an inorganic binder that is a sol–gel precursor for the same material composing the dispersed ceramic particles. The approach is demonstrated in printing objects composed of barium titanate (BTO), which is an important dielectric and piezoelectric material. This binder also enables us to achieve dispersions with high solid load that exhibits a shear-thinning rheological behavior, which is essential for direct ink writing (DIW) printing technology. The as-printed parts contain only 1 wt% organic materials, having 97.8% of the theoretical density, whereas the BTO binder crystalizes upon heating, without forming undesired secondary phases.

Over the last two decades, carbon based materials and especially carbon nanotubes (CNTs), were the subject of many studies, mainly due to their unique electrical, optical and mechanical properties (Ouyang et al., 2002; Dresselhaus et al., 2003; Dresselhaus et al., 1995). CNTs can combine electrical conductivity with wide absorption spectra, and can be produced in large scale (Danafar et al., 2009) [4]. These properties enable to realize CNTs in simple, low-cost detector. Here we present a proof-of-concept for such a detector operating at the short-wave infrared (SWIR) regime. We use a simple spray technique, which allows creating a large matrix of CNT bundles. Semiconducting quantum dots (QDs) were adsorbed on top of the CNTs, enhancing the sensitivity to the infrared regime. This regime is important for numerous applications in the civil, medical, defense and security fields. Controlled coupling between the QDs and the CNT matrix generates gate-like electro-optical response when light is absorbed. This proof-of-concept for a detector in the SWIR region is presented for large surfaces and substrates, while the responsivity and detectivity of the detector in a range of frequencies and wavelengths was evaluated.

Localization of rectal tumors is a challenge in minimally invasive surgery due to the lack of tactile sensation. We had developed liposomal indocyanine green (Lip-ICG) for localization of rectal tumor. In this study we evaluated the effects of liposome size and lipid PEGylation on imaging. We used an endoscopically-guided orthotopic experimental rectal cancer model in which tumor fluorescence was determined at different time points after intravenous (i.v.) administration of Lip-ICG and PEGylated liposomes (PEG-Lip-ICG). Signal intensity was measured by tumor-to-background ratio (TBR), or normalized TBR (compared to TBR of free ICG). Fluorescence microscopy of tumor tissue was performed to determine fluorescence localization within the tissue and blood vessels. Liposomes of 60 nm showed an increased TBR compared with free ICG at 12 hours after i.v. injection: normalized TBR (nTBR) = 3.11 vs. 1, respectively (p = 0.006). Larger liposomes (100 nm and 140 nm) had comparable signal to free ICG (nTBR = 0.98 ± 0.02 and 0.78 ± 0.08, respectively), even when additional time points were examined (0.5, 3 and 24 hours). PEG-Lip- ICG were more efficient than Lip-ICG (TBR = 4.2 ± 0.18 vs. 2.5 ± 0.12, p < 0.01) presumably because of reduced uptake by the reticulo-endothelial system. ICG was found outside the capillaries in tumor margins. We conclude that size and lipid modification impact imaging intensity.

Localization of rectal tumors is a challenge in minimally invasive surgery due to the lack of tactile sensation. We had developed liposomal indocyanine green (Lip-ICG) for localization of rectal tumor. In this study we evaluated the effects of liposome size and lipid PEGylation on imaging. We used an endoscopically-guided orthotopic exptl. rectal cancer model in which tumor fluorescence was determined at different time points after i.v. (i.v.) administration of Lip-ICG and PEGylated liposomes (PEG-Lip-ICG). Signal intensity was measured by tumor-to-background ratio (TBR), or normalized TBR (compared to TBR of free ICG). Fluorescence microscopy of tumor tissue was performed to determine fluorescence localization within the tissue and blood vessels. Liposomes of 60 nm showed an increased TBR compared with free ICG at 12 h after i.v. injection: normalized TBR (nTBR) = 3.11 vs. 1, resp. (p = 0.006). Larger liposomes (100 nm and 140 nm) had comparable signal to free ICG (nTBR = 0.98 ± 0.02 and 0.78 ± 0.08, resp.), even when addnl. time points were examined (0.5, 3 and 24 h). PEG-Lip- ICG were more efficient than Lip-ICG (TBR = 4.2 ± 0.18 vs. 2.5 ± 0.12, p < 0.01) presumably because of reduced uptake by the reticulo-endothelial system. ICG was found outside the capillaries in tumor margins. We conclude that size and lipid modification impact imaging intensity.

Fabrication of devices by printing conductive interconnections on plastic substrates is of growing interest. Currently, silver flakes are wildly used, however the high cost of silver prevents their wide use in many elec. devices. A new two-step process for synthesizing thin copper flakes, and their utilization in conductive inks, is reported. In the first step, sub-micrometer copper particles are formed by thermal decomposition and self-reduction of copper formate. These copper particles are then milled in a wet bead mill that results in their transformation into thin flakes with an average thickness of 48 nm. X-ray diffraction results indicate that the copper particles undergo plastic deformation in a mechanism similar to cold rolling. The effect of various process parameters and type of dispersing agents on the morphol. and elec. performance is studied. The ink formulations result in printed patterns with 22% of bulk copper conductivity The optimal ink is used to print functioning near field communication antennas on polyimide film, which is found to have a high bending durability.

Abstract Silver nanoparticle based microelectrodes embedded between layers of hydrogel material were successfully fabricated. 3D bioprinting is employed to print the entire bioelectronics platform comprising of conducting silver ink and Gelatin methacryloyl (GelMA) hydrogel. The additive manufacturing technique of bioprinting gives design freedom for the circuit, saves material and shortens the time to fabricate the bioelectronics platform. The silver platform shows excellent electrical conductivity, structural flexibility and stability in wet environment. It is tested for biocompatibility using C2C12 murine myoblasts cell line. The work demonstrates the potential of the fabricated platform for the realization of practical bioelectronic devices.

Hybrid organic–inorganic sol gel inks that can undergo both condensation and radical polymerization are developed, enabling fabrication of complex objects by additive manufacturing technology, yielding 3D objects with superior properties. The 3D objects have very high silica content and are printed by digital light processing commercial printers. The printed lightweight objects are characterized by excellent mechanical strength compared to currently used high-performance polymers (139 MPa), very high stability at elevated temperatures (heat deflection temperature >270 °C), high transparency (89%), and lack of cracks, with glossiness similar to silica glasses. The new inks fill the gap in additive manufacturing of objects composed of ceramics only and organic materials only, thus enabling harnessing the advantages of both worlds of materials.

A sol, aqueous solution-based ink is presented for fabrication of 3D transparent silica glass objects with complex geometries, by a simple 3D printing process conducted at room temperature. The ink combines a hybrid ceramic precursor that can undergo both the photopolymerization reaction and a sol-gel process, both in the solution form, without any particles. The printing is conducted by localized photopolymerization with the use of a low-cost 3D printer. Following printing, upon aging and densifying, the resulting objects convert from a gel to a xerogel and then to a fused silica. The printed objects, which are composed of fused silica, are transparent and have tunable density and refractive indices.

3D printed electronics is an emerging field of high importance in both academic research and industrial manufacturing. It enables fabrication of 3D devices with embedded or conformal electronic circuits, which are relevant to a variety of applications, such as Internet of things, soft robotics, and medical devices. Patterning of electrical conductors with conductivity higher than 50% bulk copper is challenging and usually involves electroless or electrolytic deposition processes that require the use of very costly catalyst, mainly palladium, as a seed material. Here, the use of a binuclear copper complex as a very efficient replacement for the conventional catalysts, which can be directly inkjet printed onto 3D plastic objects, is described. After printing, the copper complex is converted into pure copper upon short exposure to low-temperature plasma. By combining the binuclear complex with electroless plating, resistivity as low as 2.38 µΩ cm, which corresponds to a 72% conductivity of bulk copper, is obtained. The applicability of the complex ink and the process is demonstrated in the fabrication of a near-field communication antenna on a 3D printed plastic object.

Transparent conductive networks are important for flexible electronics and solar cells. Often interwire (junction) conductivity is the limiting factor for network conductivity and can be improved by various treatments. The conductivity of individual junctions in a single walled carbon nanotube network was measured by conductive atomic force microscopy before and after exposure to nitric acid. The measurements show that this exposure improves the conductivity of each one of the junctions within the network. Our results suggest that the acid improves the conductivity by p-type charge transfer doping and by surfactant degradation.

High-quality patterns were successfully prepared by inkjet-printing WO3-PEDOT:PSS composites on different substrates including the rigid FTO glass and most importantly, on flexible PEDOT:PSS/Ag grid/PET. Excellent electrochromic performances can be achieved, including large optical modulation (85.7% optical contrast at the wavelength of 633 nm on FTO glass substrate), fast switching speed (coloration/bleaching time of 2.4/0.8 s on the PEDOT:PSS/Ag grid/PET substrate), instantaneous coloration efficiency (68.8 cm2 C−1) and good cycling stability (up to 10,000 cycles). The effects of the applied potential window during electrochemical evaluation on the electrochromic performances were analyzed in detail. The printed electrochromics films on PEDOT:PSS/Ag grid/PET showed the best electrochemical stability, in agreement with its superior conductivity and transmittance at 633 nm of 0.6 Ω/sq and 66%, respectively. It sustained transmittance modulation of about 75.5% and 53.1% of its first cycle recorded contrast at 633 nm, after being subjected to 1000 and 5000 cycles, respectively, and maintained good electrochemical stability up to 10,000 cycles. Moreover, a robust mechanical stability was also achieved by the printed films on flexible PEDOT:PSS/Ag grid/PET substrate. The film maintained a transmittance modulation of 85.8% of its original contrast after 5000 bending cycles at a curvature radius of 1 cm. The inkjet-printed WO3 nanocomposite based flexible electrochromic displays exhibited excellent electrochromic performance, making it a promising candidate for energy efficient displays, e-books, e-cards and multifunctional electronic devices.

During decomposition of copper formate, a volatile intermediate is formed, that can be utilized to fabricate conductive copper lines for electrical interconnections. By the method called Reactive Transfer Printing (RTP), a pattern of copper (II) formate was printed, and placed adjacent to a second surface; decomposition of the printed pattern led to a transfer of copper to the second substrate. It was found that the yield of the transfer process improved due to presence of several carboxylic acids which are liquid with a high boiling point. Furthermore we found that the transport of copper starts at a lower temperature than previously reported, indicating that the first decomposition step of copper formate is related to the catalytic decomposition of formic acid on a copper surface. The findings enable printing of conductive copper patterns onto the interior surface of a glass vessel.

Liquid drop evaporation on surfaces is present in many industrial and medical applications, e.g., printed electronics, spraying of pesticides, DNA mapping, etc. Despite this strong interest, a theoretical description of the dynamic of the evaporation of complex liquid mixtures and nanosuspensions is still lacking. Indeed, one of the aspects that have not been included in the current theoretical descriptions is the competition between the kinetics of evaporation and the adsorption of surfactants and/or particles at the liquid/vapor and liquid/solid interfaces. Materials formed by an electrically isolating solid on which a patterned conducting layer was formed by the deposits left after drop evaporation have been considered as very promising for building electrical circuits on flexible plastic substrates. In this work, we have done an exhaustive study of the evaporation of nanosuspensions of latex and hydrophobized silver nanoparticles on four substrates of different hydrophobicity. The advancing and receding contact angles as well as the time dependence of the volume of the droplets have been measured over a broad range of particle concentrations. Also, mixtures of silver particles and a surfactant, commonly used in industrial printing, have been examined. Furthermore, the adsorption kinetics at both the air/liquid and solid/liquid interfaces have been measured. Whereas the latex particles do not adsorb at the solid/liquid and only slightly reduce the surface tension, the silver particles strongly adsorb at both interfaces. The experimental results of the evaporation process were compared with the predictions of the theory of Semenov et al. (Evaporation of Sessile Water Droplets: Universal Behavior in the Presence of Contact Angle Hysteresis. Colloids Surf. Physicochem. Eng. Asp. 2011, 391 (1-3), 135-144) and showed surprisingly good agreement despite that the theory was developed for pure liquids. The morphology of the deposits left by the droplets after total evaporation was studied by scanning electronic microscopy, and the effects of the substrate, the particle nature, and their concentrations on these patterns are discussed.