Unlocking Spatial Surface Energy in Porous Skeletons: A Pathway to Bridging Electronic Circuits from 2D to 3D Architectures.

Conventional approaches to creating high-resolution electric circuits face challenges such as the requirement for skilled personnel and expensive equipment. In response, we propose an innovative strategy that leverages a photochemically modified porous polymer skeleton for in-situ circuit fabrication. By developing maskless surface energy manipulation that guides PEDOT:PSS-based conductive ink deposition, electric circuits with high precision, density, stability and adaptability are effortlessly engineered within or atop the porous skeleton, enabling transitions between 2D and 3D circuit configurations. This process simplifies prototyping while significantly reducing costs and maintaining efficiency, promising advancements across various technological sectors.

Blade-Coating (100)-Oriented α-FAPbI3 Perovskite Films via Crystal Surface Energy Regulation for Efficient and Stable Inverted Perovskite Photovoltaics.

Photoactive formamidinium lead triiodide (α-FAPbI3) perovskite has dominated the prevailing high-performance perovskite solar cells (PSCs), normally for those spin-coated, conventional n-i-p structured devices. Unfortunately, α-FAPbI3 has not been made full use of its advantages in inverted p-i-n structured PSCs fabricated via blade-coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol% of N-aminoethylpiperazine hydroiodide (NAPI) additive into α-FAPbI3 crystal-derived perovskite ink, which enabled the formation of phase-pure, highly-oriented α-FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade-coated α-FAPbI3 perovskite films via combining a series of in-situ characterizations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb-I framework help to reduce the surface energy of (100) crystal plane by 42%, retard the crystallization rate and lower the formation energy of α-FAPbI3. The resultant blade-coated inverted PSCs based on (100)-oriented α-FAPbI3 perovskite films realized promising efficiencies up to 24.16% (~26.5% higher than that of the randomly-oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3-based inverted PSCs fabricated via scalable deposition methods.

All-Solution-Processed Electronics with Sub-Microscale Resolution and Nanoscale Fidelity Fabricated Via a Humidity-Controlled, Surface Energy-Directed Assembly Process.

Solution-based processes have received considerable attention in the fabrication of electronics and sensors owing to their merits of being low-cost, vacuum-free, and simple in equipment. However, the current solution-based processes either lack patterning capability or have low resolution (tens of micrometers) and low pattern fidelity in terms of line edge roughness (LER, several micrometers). Here, we present a surface energy-directed assembly (SEDA) process to fabricate metal oxide patterns with up to 2 orders of magnitude improvement in resolution (800 nm) and LER (16 nm). Experiment results show that high pattern fidelity can be achieved only at low relative humidities of below 30%. The reason for this phenomenon lies in negligible water condensation on the solution droplet. Employing the SEDA process, all-solution-processed metal oxide thin film transistors (TFTs) are fabricated by using indium oxide as channel layers, indium tin oxide as source/drain electrodes and gate electrodes, and aluminum oxide as gate dielectrics. TFT-based logic gate circuits, including NOT, NOR, NAND, and AND are fabricated as well, demonstrating the applicability of the SEDA process in fabricating large area functional electronics.

Thermal Surface Properties, London Dispersive and Polar Surface Energy of Graphene and Carbon Materials Using Inverse Gas Chromatography at Infinite Dilution.

The thermal surface properties of graphenes and carbon materials are of crucial importance in the chemistry of materials, chemical engineering, and many industrial processes. BACKGROUND: The determination of these surface properties is carried out using inverse gas chromatography at infinite dilution, which leads to the retention volume of organic solvents adsorbed on solid surfaces. This experimental and fundamental parameter actually reflects the surface thermodynamic interactions between injected probes and solid substrates. METHODS: The London dispersion equation and the Hamieh thermal model are used to quantify the London dispersive and polar surface energy of graphenes and carbon fibers as well their Lewis acid-base constants by introducing the coupling amphoteric constant of materials. RESULTS: The London dispersive and polar acid-base surface energies, the free energy of adsorption, the polar enthalpy and entropy, and the Lewis acid-base constants of graphenes and carbon materials are determined. CONCLUSIONS: It is shown that graphene exhibited the highest values of London dispersive surface energy, polar surface energy, and Lewis acid-base constants. The highest characteristics of graphene justify its great potentiality and uses in many industrial applications.

Effect of surface treatment strategies on bond strength of additively and subtractively manufactured hybrid materials for permanent crowns.

OBJECTIVES: The purpose of this study is to evaluate the bond strength of different computer-aided design / computer-aided manufacturing (CAD/CAM) hybrid ceramic materials following different pretreatments. METHODS: A total of 306 CAD/CAM hybrid material specimens were manufactured, n = 102 for each material (VarseoSmile Crownplus [VSCP] by 3D-printing; Vita Enamic [VE] and Grandio Blocs [GB] by milling). Each material was randomly divided into six groups regarding different pretreatment strategies: control, silane, sandblasting (50 µm aluminum oxide particles), sandblasting + silane, etching (9% hydrofluorics acid), etching + silane. Subsequently, surface roughness (Ra) values, surface free energy (SFE) were measured. Each specimen was bonded with a dual-cured adhesive composite. Half of the specimens were subjected to thermocycling (5000 cycles, 5-55 °C). The shear bond strength (SBS) test was performed. Data were analyzed by using a two-way analysis of variance, independent t-test, and Mann-Whitney-U-test (α = 0.05). RESULTS: Material type (p = 0.001), pretreatment strategy (p < 0.001), and the interaction (p < 0.001) all had significant effects on Ra value. However, only etching on VSCP and VE surface increased SFE value significantly. Regarding SBS value, no significant difference was found among the three materials (p = 0.937), while the pretreatment strategy significantly influenced SBS (p < 0.05). Etching on VSCP specimens showed the lowest mean value among all groups, while sandblasting and silane result in higher SBS for all test materials. CONCLUSIONS: The bond strength of CAD/CAM hybrid ceramic materials for milling and 3D-printing was comparable. Sandblasting and silane coupling were suitable for both millable and printable materials, while hydrofluoric etching should not be recommended for CAD/CAM hybrid ceramic materials. CLINICAL RELEVANCE: Since comparable evidence between 3D-printable and millable CAD/CAM dental hybrid materials is scarce, the present study gives clear guidance for pretreatment planning on different materials.

Effect of universal adhesive pretreatments on the bond strength durability of conventional and adhesive resin cements to zirconia ceramic.

PURPOSE: This study aimed to evaluate the effect of pretreatment of three different universal adhesives (Single Bond Universal [SBU], All-Bond Universal [ABU], and Prime&Bond universal [PBU]) on the bonding durability of an adhesive (Panavia F 2.0, PF) and a conventional (Duo-Link, DL) resin cements to air-abraded zirconia. MATERIALS AND METHODS: Rectangular-shaped zirconia specimens were prepared. The chemical composition and surface energy parameters of the materials were studied by Fourier transform infrared spectroscopy and contact angle measurement, respectively. To evaluate resin bonding to the zirconia, all the bonding specimens were immersed in water for 24 h and the specimens to be aged were additionally thermocycled 10000 times before the shear bond strength (SBS) test. RESULTS: The materials showed different surface energy parameters, including the degree of hydrophilicity/hydrophobicity. While the DL/CON (no pretreatment) showed the lowest SBS and a significant decrease in the value after thermocycling (P < .001), the PF/CON obtained a higher SBS value than the DL/CON (P < .001) and no decrease even after thermocycling (P = .839). When the universal adhesives were used with DL, their SBS values were higher than the CON (P < .05), but the trend was adhesive-specific. In conjunction with PF, the PF/SBU produced the highest SBS followed by the PF/ABU (P = .002), showing no significant decrease after thermocycling (P > .05). The initial SBS of the PF/PBU was similar to the PF/CON (P = .999), but the value decreased after thermocycling (P < .001). CONCLUSION: The universal adhesive pretreatment did not necessarily show a synergistic effect on the bonding performance of an adhesive resin cement, whereas the pretreatment was beneficial to bond strength and durability of a conventional resin cement.

Effect of Al and Mn substitutions on hydrogen activation performances of La-Ni-Al-Mn alloy.

To interpret the effect of Al and Mn substitutions on activation performances of La-Ni-Al-Mn alloy, the initial activation curve has been measured, which shows that the incubation time of activation is prolonged with the increase of Al content in alloy, while shortened duo to Mn substitution. Further, the first-principles calculations are employed. We find that (1) (100)/(010) surface of LaNi5 is the most stable and its stability can be improved by Al substitution for Ni while decreased by Mn substitution; (2) the preferential hydrogen adsorption sites are the hole and Ni (or Mn)-top sites; (3) Al and Mn substitutions can increase the hydrogen adsorption stability, but Al doping decreases the number of available sites, therefore retarding activation, while Mn doping guarantees the number of available sites, making activation easier; (4) H bonds covalently with neighbor Ni (or Mn) and ionically with La, together determining the stability of hydrogen adsorption.

Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.

Medium-Entropy Monosilicates Deliver High Corrosion Resistance to Calcium-Magnesium Aluminosilicate Molten Salt.

For decreasing the global cost of corrosion, it is essential to understand the intricate mechanisms of corrosion and enhance the corrosion resistance of materials. However, the ambiguity surrounding the dominant mechanism of calcium-magnesium aluminosilicate (CMAS) molten salt corrosion in extreme environments hinders the mix-and-matching of the key rare earth elements for increasing the resistance of monosilicates against corrosion of CMAS. Herein, an approach based on correlated electron microscopy techniques combined with density functional theory calculations is presented to elucidate the complex interplay of competing mechanisms that control the corrosion of CMAS of monosilicates. These findings reveal a competition between thermodynamics and kinetics that relies on the temperatures and corrosion processes. Innovative medium-entropy monosilicates with exceptional corrosion resistance even at 1500 °C are developed. This is achieved by precisely modulating the radii of rare earth ions in monosilicates to strike a delicate balance between the competition in thermodynamics and kinetics. After 50 and 100 h of corrosion, the thinnest reactive layers are measured to be only 28.8 and 35.4 µm, respectively.

Surface Energy-Assisted Patterning of Vapor Deposited All-Inorganic Perovskite Arrays for Wearable Optoelectronics.

Solution-based methods for fabricating all-inorganic perovskite film arrays often suffer from limited control over nucleation and crystallization, resulting in poor homogeneity and coverage. To improve film quality, advanced vapor deposition techniques are employed for continuous film. Here, the vapor deposition strategy to the all-inorganic perovskite films array, enabling area-selective deposition of perovskite through substrate modulation is expanded. It can yield a high-quality perovskite film array with different pixel shapes, various perovskite compositions, and a high resolution of 423 dpi. The resulting photodetector arrays exhibit remarkable optoelectronic performance with an on/off ratio of 13 887 and responsivity of 47.5 A W-1. The device also displays long-term stability in a damp condition for up to 12 h. Moreover, a pulse monitoring sensor based on the perovskite films array demonstrates stable monitoring for pulse signals after being worn for 12 h and with a low illumination of 0.055 mW cm-2, highlighting the potential application in wearable optoelectronic devices.

Cotton fabrics modified with tannic acid/1-eicosanamine grafting layer for oil/water separation.

The wettability of the surface of hydrophilic cotton fabrics was modified using a one-step protocol with tannic acid (TA) to provide its excess catechol groups to be grafted with 1-eicosanamine at pH 8.5 and room temperature with catalysts CuSO4/H2O2. The modification over the synthesis conditions revised the contact angles of water and diiodomethane droplets from 132.68 ± 0.49° to 143.95 ± 0.80° and from 100.08°±1.42° to 82.96 ± 1.38°, respectively. The corresponding dispersive of the so-yielded cotton surface ranged from 8.6 to 16.0 mJ/m2, and the polar components ranged from 0.08 to 2.7 mJ/m2, much lower than polytetrafluoroethylene. The modified cotton fabrics are omniphobic and can repel water and commercial oil products. The absorption tests revealed that the modified cotton fabrics absorbed 1.10 g hexane/g cotton by contacting hexane (top)-water (bottom) layers and absorbed 1.26 g hexane/g cotton by contacting water first for 30 s, then hexane for another 30 s. The modified fabrics reveal good absorption reusability as hexane absorbent is even pre-saturated with water. This conclusion is also valid for commercial unleaded gasoline #95 and diesel. A parametric study revealed that the added catalysts and prolonged reaction time would enhance the hydrophobicity of the surface. These modified cotton fabrics can absorb oil from water and oil spills. Mechanisms corresponding to this observation are discussed.

New Progress on London Dispersive Energy, Polar Surface Interactions, and Lewis's Acid-Base Properties of Solid Surfaces.

The determination of the polar surface free energy, polar properties, and Lewis's acid base of solid materials is of capital importance in many industrial processes, such as adhesion, coatings, two-dimensional films, and adsorption phenomena. (1) Background: The physicochemical properties of many solid particles were characterized during the last forty years by using the retention time of injected well-known molecules into chromatographic columns containing the solid substrates to be characterized. The obtained net retention time of the solvents adsorbed on the solid, allowing the determination of the net retention volume directly correlated to the specific surface variables, dispersive, polar, and acid-base properties. (2) Methods: Many chromatographic methods were used to quantify the values of the different specific surface variables of the solids. However, one found a large deviation between the different results. In this paper, one proposed a new method based on the London dispersion equation that allowed the quantification of the polar free energy of adsorption, as well as the Lewis's acid-base constants of many solid surfaces. (3) Results: The newly applied method allowed us to obtain the polar enthalpy and entropy of adsorption of polar model organic molecules on several solid substrates, such as silica, alumina, MgO, ZnO, Zn, TiO2, and carbon fibers. (4) Conclusions: our new method based on the separation between the dispersive and polar free surface energy allowed us to better characterize the solid materials.

Hygroscopy as an Indicator of Specific Surface Area in Polymer Materials.

Specific surface area (SSA) is an integral characteristic of the interfacial surface in poly-disperse systems, widely used for the assessment of technological properties in polymer materials and composites. Hygroscopic water content (Wh) is an obligate indicator of dispersed materials prior to any analysis of their chemical composition. This study links both indicators for the purpose of the express assessment of SSA using widely available Wh data, on the example of natural (starch, cellulose) and synthetic (acrylic hydrogels) polymer materials. The standard BET analysis of SSA using water vapor desorption was chosen as a reference method. In contrast to the known empirical correlations, this study is based on the fundamental thermodynamic theory of the disjoining water pressure for the connection of the analyzed quantities. The statistical processing of the results for the new methodology and the standard BET method showed their good compliance in a wide range of SSA from 200 to 900 m2/g. The most important methodological conclusion is the possibility of an accurate physically based calculation of hydrophilic SSA in polymer materials using their Wh data at a known relative humidity in the laboratory.

Seaweed-inspired underwater anti-oil-fouling and anti-fogging coating with mechanical durability.

Ecofriendly fabrication of anti-oil-fouling materials is of interest. Surfaces with underwater superoleophobicity have been fabricated which exhibit limited mechanical durability and water resistance. In this study, we report on a bioinspired bilayer design of a transparent anti-oil-fouling coating. Seaweed surfaces show anti-oil-fouling in the sea due to its high surface hydration ability. Mussels can adhere tightly onto a surface with good stability in the sea by virtue of its levodopa-containing secretions. The surface layer was fabricated using a crosslinked combination of carboxymethyl cellulose (CMC) and sodium alginate (AlgS) inspired by seaweed, with the addition of calcium ions. Polydopamine (PDA), a derivative of levodopa, was used as the underlayer to enhance bonding strength and water resistance. Oil that adhered to the coated surface was spontaneously detached upon immersion in water. The mechanism underlying this anti-oil-fouling effect was elucidated using Gibbs free energy theory. The coating exhibited mechanical durability and water resistance. The coating is transparent and preserves the original color of the substrate. The coated glass showed stable anti-fogging and anti-frost performance. These coatings hold promise for a wide range of anti-oil-fouling applications.

Growth Control of InP/ZnSe Heterostructured Nanocrystals.

The morphology of heterostructured semiconductor nanocrystals (h-NCs) dictates the spatial distribution of charge carriers and their recombination dynamics and/or transport, which are the main performance indicators of photonic applications utilizing h-NCs. The inability to control the morphology of heterovalent III-V/II-VI h-NCs composed of heavy-metal-free elements hinders their practical use. As a case study of III-V/II-VI h-NCs, the growth control of ZnSe epilayers on InP NCs is demonstrated here. The anisotropic morphology in InP/ZnSe h-NCs is attributed to the facet-dependent energy costs for the growth of ZnSe epilayers on different facets of InP NCs, and effective chemical means for controlling the growth rates of ZnSe on different surface planes are demonstrated. Ultimately, this article capitalizes on the controlled morphology of InP/ZnSe h-NCs to expand their photophysical characteristics from stable and pure emission to environment-sensitive one, which will facilitate their use in a variety of photonic applications.

Photoluminescence variations in organic fluorescent crystals by changing the surface energy of the substrate.

Organic fluorescent crystals were obtained using single-benzene-based diethyl 2,5-dihydroxyterephthalate (DDT) molecules through crystallization from a droplet of the DDT solution on an Au substrate. To control the size of the DDT crystals, the surface energy of the Au substrate was modified with air plasma treatment, producing a hydrophilic surface and a hydrophobic self-assembled monolayer (SAM) coating. The size of DDT crystals increased as the surface energy of the substrate decreased. The averaged cross-section area of the DDT crystals on the Au substrates increased in the order of the air-plasma-treated substrate (∼23.43 µm2) < pristine substrate (∼225.6 µm2) < hydrophobic SAM-coated substrate (∼2240 µm2). On the other hand, the main emission of the DDT crystals redshifted from blue to green as the crystal size increased, which is related to the aggregation of the DDT crystals. Moreover, the coffee-ring effect during the DDT crystallization was hindered by controlling the solvent evaporation conditions. As examples of the application of the proposed technique, patterned DDT crystals were obtained using selectively patterned hydrophobic and hydrophilic substrates.

Application of Surface Stress-Driven Model for Higher Vibration Modes of Functionally Graded Nanobeams.

This paper employs a surface stress-driven nonlocal theory to investigate the synergistic impact of long-range interaction and surface energy on higher vibration modes of Bernoulli-Euler nanobeams made of functionally graded material. It takes into account surface effects such as the surface modulus of elasticity, residual surface stresses, surface density, and rotary inertia. The governing equation is derived through the application of Hamilton's principle. The novelty of this work lies in its pioneering approach to studying higher-order vibrations, carefully considering the combination of long-range interactions and surface energy in nanobeams of functionally graded materials through a well-posed mathematical model of nonlocal elasticity. This study conducts a parametric investigation, examining the effects of the nonlocal parameter and the material gradient index for four static schemes: Cantilever, Simply-Supported, Clamped-Pinned and Clamped-Clamped nanobeams. The outcomes are presented and discussed, highlighting the normalized nonlocal natural frequencies for the second through fifth modes of vibration in each case under study. In particular, this study illustrates the central role of surface effects in the dynamic response of nanobeams, emphasizing the importance of considering them. Furthermore, the parametric analysis reveals that the dynamic response is influenced by the combined effects of the nonlocal parameter, the material gradient index, the shapes of the cross-sections considered, as well as the static scheme analyzed.

3D Printing Architecting ß-PVDF Reservoirs for Preferential ZnO Epitaxial Growth Toward Advanced Piezoelectric Energy Harvesting.

For polyvinylidene fluoride (PVDF) based piezoelectric composites, epitaxial growth of ZnO nanorods (ZnO-nr) piezoceramic layer on PVDF is an effective way to improve their piezoelectric performance. However, the crystal nucleus of ZnO featuring polar surfaces that cannot be directly attached to hydrophobic PVDF with low surface energy. Herein, direct ink writing (DIW) 3D printing is employed for the first time to create ß-PVDF reservoirs with significantly enhanced surface energy, facilitating the attachment and epitaxial growth of ZnO-nr. The printed ß-PVDF reservoirs designed with programmed macro-pores and abundant inner micropores, enable a higher loading of ZnO-nr by more than one magnitude, thereby boosting the electro-mechanical response. The resulting PVDF/ZnO core-shell piezoelectric energy harvester (PEH) delivers an output voltage of 33.2 V, as well as an unprecedentedly high relative output voltage of 2.76 V/wt.%, which is 2.63 times that of the state-of-the-art 3D-printed PVDF/piezoceramics PEHs. Furthermore, it can differentiate subtle human motions whereas hybrid PEHs cannot distinct. This work demonstrates that the DIW 3D printing approach offers a simple and convenient design idea for creating high performance PEHs.

Preferential growth and electron trap synergistically promoting photoreduction CO2 of Tm ion doping bismuth titanate nanosheets.

In this study, we prepared two-dimensional Bi4Ti3O12 nanosheets doped with rare earth ions. The experimental results show that Bi4-xTmxTi3O12 exhibits the highest reduction performance among various rare earth doped Bi4Ti3O12 materials, with a CO yield of 7.25 µmol g-1h-1. Furthermore, a delayed reaction in Bi3.97Tm0.03Ti3O12 is observed upon a cessation of light irradiation. Theoretical calculations reveal that the introduction of Tm ion not only reduces the surface energy of (001) plane and make it preferential growth in Bi4Ti3O12, but also brings the intervening energy level of Tm ion (4f and 4d mixed orbital), which is closer to the conduction band of Bi4Ti3O12 and facilitates charge carrier accumulation in trap states. The electrons retained in the shallow traps promote the hysteresis reaction following a cessation of illumination. This work provides further insights into elucidating precise reduction reaction mechanisms underlying rare earth dopant on photocatalysts. This research provides enhanced insights into unraveling the precise reduction reaction mechanisms influenced by rare earth dopants in photocatalysts.

Kinetics Controlled Perovskite Crystallization for High Performance Solar Cells.

The power conversion efficiencies (PCEs) of perovskite solar cells have recently developed rapidly compared to crystalline silicon solar cells. To have an effective way to control the crystallization of perovskite thin films is the key for achieving good device performance. However, a paradox in perovskite crystallization is from the mismatch between nucleation and Oswald ripening. Usually, the large numbers of nucleation sites tend to weak Oswald ripening. Here, we proposed a new mechanism to promote the formation of nucleation sites by reducing surface energy from 44.9 mN/m to 36.1 mN/m, to spontaneously accelerate the later Oswald ripening process by improving the grain solubility through the elastic modulus regulation. The ripening rate is increased from 2.37 Åm ⋅ s-1 to 4.61 Åm ⋅ s-1 during annealing. Finally, the solar cells derived from the optimized films showed significantly improved PCE from 23.14 % to 25.32 %. The long-term stability tests show excellent thermal stability (the optimized device without encapsulation maintaining 82 % of its initial PCE after 800 h aging at 85 °C) and an improved light stability under illumination. This work provides a new method, the elastic modulus regulation, to enhance the ripening process.