Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization.

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs-in particular, optically clear adhesives for electronics.

Redox-Initiated Reversible Addition-Fragmentation Chain Transfer (RAFT) Miniemulsion Polymerization of Styrene using PPEGMA-Based Macro-RAFT Agent.

Redox-initiated reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerizations are successfully conducted with an employment of trithiocarbonate-based macro-RAFT agents and surfactant. Two macro-RAFT agents-hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA27 ) and amphiphilic poly(poly(ethylene glycol) methyl ether methacrylate)-b-polystyrene (PPEGMA27 -b-PS33 )- are examined for the miniemulsion polymerization of styrene. The use of PPEGMA27 (in the presence of sodium dodecyl sulfate (SDS)) results in a slow polymerization rate with a broad particle size. In the absence of SDS, the use of PPEGMA27 -b-PS33 results in a broad particle size distribution due to its inability to form uniform initial droplets whereas the same amphiphilic block copolymer in the presence of SDS yields resulting products with a uniform particle size distribution. The latter exhibits a fashion of controlled polymerization with a high consumption of monomer (98% in 100 min) and a narrow molecular weight distribution throughout the polymerization. This is attributed to the formation of uniform droplets facilitated by SDS in a miniemulsion. The amphiphilic macro-RAFT agent is able to anchor efficiently on the monomer droplet or particle/water interface and form stabilized particles of well-defined PPEGMA27 -b-PS block copolymer, confirmed using dynamic light scattering and transmission electron micrographs.

Exploiting Dynamic Opening of Apertures in a Partially Fluorinated MOF for Enhancing H2 Desorption Temperature and Isotope Separation.

Deuterium has been recognized as an irreplaceable element in industrial and scientific research. However, hydrogen isotope separation still remains a huge challenge due to the identical physicochemical properties of the isotopes. In this paper, a partially fluorinated metal-organic framework (MOF) with copper, a so-called FMOFCu, was investigated to determine the separation efficiency and capacity of the framework for deuterium extraction from a hydrogen isotope mixture. The unique structure of this porous material consists of a trimodal pore system with large tubular cavities connected through a smaller cavity with bottleneck apertures with a size of 3.6 Å plus a third hidden cavity connected by an even smaller aperture of 2.5 Å. Depending on the temperature, these two apertures show a gate-opening effect and the cavities get successively accessible for hydrogen with increasing temperature. Thermal desorption spectroscopy (TDS) measurements indicate that the locally flexible MOF can separate D2 from anisotope mixture efficiently, with a selectivity of 14 at 25 K and 4 at 77 K.

A facile and rapid process to fabricate platinum counter electrode in dye-sensitized solar cell using nanosecond pulsed laser sintering at room temperature.

To fabricate the platinum (Pt) counter electrode in dye-sensitized solar cells (DSSCs), rapid and low sintering process was carried out using nanosecond pulsed laser sintering (LS) method based on third harmonic (355 nm) of an Nd:YAG laser at room temperature. The surface morphology of LS-Pt on fluorine-doped tin oxide (FTO) electrode showed thin and compact structure, consisting of particles size of - 10-30 nm and thickness of below 30 nm. The DSSCs with the LS-Pt/FTO counter electrodes displayed the power conversion efficiency of 4.4% with short-circuit current = 9.07 mA/cm2, open-circuit voltage = 0.79 V and fill factor = 61.3.

Biomass-Derived Optically Clear Adhesives for Foldable Displays.

Novel acrylate monomers, derived from terpenes are synthesized for use in optically clear adhesives (OCAs) suitable for foldable displays. These OCAs are prepared using visible-light-driven polymerization, an eco-friendly method. Through physical, rheological, and mechanical characterization, the prepared OCAs possess low modulus and exhibit outstanding creep and recovery properties, making them suitable for foldable devices.

Visible-Light-Driven Rapid 3D Printing of Photoresponsive Resins for Optically Clear Multifunctional 3D Objects.

Light-driven 3D printing is gaining significant attention for its unparalleled build speed and high-resolution in additive manufacturing. However, extending vat photopolymerization to multifunctional, photoresponsive materials poses challenges, such as light attenuation and interference between the photocatalysts (PCs) and photoactive moieties. This study introduces novel visible-light-driven acrylic resins that enable rapid, high-resolution photoactive 3D printing. The synergistic combination of a cyanine-based PC, borate, and iodonium coinitiators (HNu 254) achieves an excellent printing rate and feature resolution under low-intensity, red light exposure. The incorporation of novel hexaarylbiimidazole (HABI) crosslinkers allows for spatially-resolved photoactivation upon exposure to violet/blue light. Furthermore, a photobleaching mechanism inhibited by HNu 254 during the photopolymerization process results in the production of optically-clear 3D printed objects. Real-time Fourier transform infrared spectroscopy validates the rapid photopolymerization of the HABI-containing acrylic resin, whereas mechanistic evaluations reveal the underlying dynamics that are responsible for the rapid photopolymerization rate, wavelength-orthogonal photoactivation, and observed photobleaching phenomenon. Ultimately, this visible-light-based printing method demonstrates: (i) rapid printing rate of 22.5 mm h-1, (ii) excellent feature resolution (≈20 µm), and (iii) production of optically clear object with self-healing capability and spatially controlled cleavage. This study serves as a roadmap for developing next-generation "smart" 3D printing technologies.

Iterative SuFEx approach for sequence-regulated oligosulfates and its extension to periodic copolymers.

The synthesis of sequence-regulated oligosulfates has not yet been established due to the difficulties in precise reactivity control. In this work, we report an example of a multi-directional divergent iterative method to furnish oligosulfates based on a chain homologation approach, in which the fluorosulfate unit is regenerated. The oligosulfate sequences are determined by high resolution mass spectrometry of the hydrolyzed fragments, and polysulfate periodic copolymers are synthesized by using oligomeric bisfluorosulfates in a bi-directional fashion. The synthetic utility of this iterative ligation is demonstrated by preparing crosslinked network polymers as synthetic adhesive materials.

Hexagonally ordered nanoparticles templated using a block copolymer film through Coulombic interactions.

We present a novel and simple method for forming hexagonal gold nanoparticle arrays that uses Coulombic interactions between negatively charged gold nanoparticles on positively charged vertically oriented poly(4-vinylpyridine) cylinders formed in a spin cast polystyrene-b-poly(4-vinylpyridine) block copolymer film. Exposure of the block copolymer film to dibromobutane vapor quaternizes and crosslinks the poly(4-vinylpyridine) domains which allows for the templated deposition of gold nanoparticles into a self-assembled hexagonal array through electrostatic interactions. These systems can form the basis for sensors or next generation nanoparticle based electronics.

Enhancement of electrochemical detection performance towards 2,4,6-trinitrotoluene by a bottom layer of ZnO nanorod arrays.

The ZnO nanostructure layers have been widely investigated as electrodes for sensors due to their intrinsic advantages such as high active area and low cost. In this work, to enhance the detection properties of ZnO nanostructural electrodes, self-organized ZnO nanorod arrays were synthesized using the chemical bath deposition (CBD) method on FTO glasses and ZnO nanoparticles. The fabricated ZnO electrodes on the two different substrates were characterized by SEM, TEM, XRD, and XPS. Subsequently, the detection performance of ZnO nanorod electrodes was electrochemically measured in a 2,4,6-trinitrotoluene (2,4,6-TNT) solution by CV and EIS. The differences in current densities between the ZnO electrodes were determined by the width of the ZnO nanorods, resulting in a ∼45% higher detection efficiency with F-CBD (the ZnO nanorods on FTO) electrodes compared to S-CBD (the ZnO nanorods on ZnO nanoparticles) electrodes.

Realizing Cross-linking-free Acrylic Pressure-Sensitive Adhesives with Intensive Chain Entanglement through Visible-Light-Mediated Photoiniferter-Reversible Addition-Fragmentation Chain-Transfer Polymerization.

A versatile and simplified synthesis scheme for intensively entangled acrylic pressure-sensitive adhesives (PSAs) was developed in this study by leveraging visible-light-driven controlled radical polymerization (photoiniferter/reversible addition-fragmentation chain-transfer polymerization) of acrylic copolymers under a controlled manner; the approach was differentiated by a single factor; molecular weight (Mw up to 2.8 MDa) with identical compositions. By manipulating Mw up to ultra-high ranges, PSAs with diversified viscoelastic properties were prepared and then assessed with a focus on realizing PSAs with a maximized degree of entanglement per chain through domination of high Mw contents, to help achieve excellent cohesiveness without a reinforcing cross-linking network. Moreover, fully linear solvent-soluble poly(acrylate)s were synthesized to facilitate reprocessing and reuse, highlighting the sustainability of the devised method and, consequently, its potential to be applied for effectively reducing industrial or daily waste.

Facile and Efficient Production of Biomass-Derived Isosorbide Dioxides via Epoxidation Using In situ-generated DMDO under Ultrasonication.

Herein, we present a facile synthetic process for producing biomass-derived isosorbide (ISB) dioxides using dimethyl dioxirane (DMDO) as an efficient oxidizing agent, which was generated in situ from acetone and KHSO5 . To achieve high conversion and product yield, the KHSO5 concentration, KHSO5 flow rate, and reaction temperature were optimized. Under the optimal conditions, rapid and efficient epoxidation using the in situ-generated DMDO was observed under ultrasonication, yielding the desired product within 35 min at 0 °C. This study offers a convenient and efficient method for generating biomass-derived ISB building blocks, which have significant potential for the fabrication of bioplastics.

Visible-Light-Curable Acrylic Resins toward UV-Light-Blocking Adhesives for Foldable Displays.

Current technological advances in the organic light-emitting diode panel design of foldable smartphones demand advanced adhesives with UV-blocking abilities, beyond their conventional roles of bonding objects and relieving deformation stress. However, optically clear adhesives (OCAs) with UV-blocking ability cannot be prepared using conventional UV-curing methods relying on a photoinitiator. Herein, a new acrylic resin that can be efficiently cured using visible light without oxygen removal is presented, which may be used to develop UV-blocking OCAs for use in current flexible displays. A novel photocatalyst and a specific combination of additives facilitate sufficiently rapid curing under visible light in the presence of UV-absorbers. Only a very small amount of the highly active photocatalyst is required to prepare UV-blocking OCA films with very high transparency in the visible region. Using this system, a UV-blocking OCA that nearly meets the specifications of an OCA used in commercialized foldable smartphones is realized. This technology can also be utilized in other applications that require highly efficient visible light curing, such as optically clear resins, dental resins, and 3D/4D-printable materials.

Robust 2D layered MXene matrix-boron carbide hybrid films for neutron radiation shielding.

Large-scale fabrication of neutron-shielding films with flexible or complex shapes is challenging. Uniform and high boron carbide (B4C) filler loads with sufficient workability are needed to achieve good neutron-absorption capacity. Here, we show that a two-dimensional (2D) Ti3C2Tx MXene hybrid film with homogeneously distributed B4C particles exhibits high mechanical flexibility and anomalous neutron-shielding properties. Layered and solution-processable 2D Ti3C2Tx MXene flakes serve as an ideal robust and flexible matrix for high-content B4C fillers (60 wt.%). In addition, the preparation of a scalable neutron shielding MXene/B4C hybrid paint is demonstrated. This composite can be directly integrated with various large-scale surfaces (e.g., stainless steel, glass, and nylon). Because of their low thickness, simple and scalable preparation method, and an absorption capacity of 39.8% for neutrons emitted from a 241Am-9Be source, the 2D Ti3C2Tx MXene hybrid films are promising candidates for use in wearable and lightweight applications.

Suppressed recombination in quantum dot-sensitized solar cells with blocking layers on FTO substrates.

The compact and thin TiO2 blocking layers (c-TiO2) were formed on F-doped SnO2 (FTO) substrate in quantum dots-sensitized solar cells (QSSCs) by chemical deposition. The c-TiO2 layers induced indirect contact between electrolyte and FTO electrode, which reduced leakage in QSSCs. The QSSCs showed power conversion efficiency (Eff) of 3.85% in the presence of c-TiO2 layers which leads to 21% improved compared to that without c-TiO2 layers (Eff = 3.18%). The presence of the c-TiO2 layers in QSSCs also improved the stability under illumination.

In situ polymerization of acetylene polymer on single-walled carbon nanotube and its application to photoinduced charge transfer system.

An acetylene polymer is formed on single-walled carbon nanotubes (SWNTs) using in situ polymerization. The acetylene polymers/SWNTs composite is hydrophilic even water-soluble, and has a structure of donor/acceptor dyad. In measurements of photocurrents-voltage curves, the composite film exhibits a power conversion efficiency of 1.50 x 10(-2%) under illumination (I = 80 mW/cm2, air mass 1.5 condition).

Structural and optical properties of chemically deposited CuInSe2 thin film in acidic medium.

Thin films of nanocrystalline CuInSe2 were prepared on glass substrates using chemical bath deposition in acidic medium at room temperature. Thickness of the chemically deposited CuInSe2 thin films was approximately 100 nm which composed of closely packed irregular grains of approximately 100-120 nm in diameter. X-ray diffraction pattern of CuInSe2 thin films showed nanocrystalline structure with (112) preferential orientation. The films exhibited faint black and direct band gap energy was 0.96 eV.

Artificial Neural Networks for Predicting Plastic Anisotropy of Sheet Metals Based on Indentation Test.

This paper mainly proposes two kinds of artificial neural network (ANN) models for predicting the plastic anisotropy properties of sheet metal using spherical indentation test, which minimizes measurement time, costs, and simplifies the process of obtaining the anisotropy properties than the conventional tensile test. The proposed ANN models for predicting anisotropic properties can replace the traditional complex dimensionless analysis. Moreover, this paper is not limited to the prediction of yield strength anisotropy but also further accurately predicts the Lankford coefficient in different orientations. We newly construct an FE spherical indentation model, which is suitable for sheet metal in consideration of actual compliance. To obtain a large dataset for training the ANN, the constructed FE model is utilized to simulate pure and alloyed engineering metals with one thousand elastoplastic parameter conditions. We suggest the specific variables of the residual indentation mark as input parameters, also with the indentation load-depth curve. The profile of the residual indentation, including the height and length in different orientations, are used to analyze the anisotropic properties of the material. Experimental validations have been conducted with three different sheet alloys, TRIP1180 steel, zinc alloy, and aluminum alloy 6063-T6, comparing the proposed ANN model and the uniaxial tensile test. In addition, machine vision was used to efficiently analyze the residual indentation marks and automatically measure the indentation profiles in different orientations. The proposed ANN model exhibits remarkable performance in the prediction of the flow curves and Lankford coefficient of different orientations.

Numerical Simulation of the Effects of Scanning Strategies on the Aluminum Evaporation of Titanium Alloy in the Electron Beam Cold Hearth Melting Process.

In the production of titanium alloy, the electron beam cold hearth melting (EBCHM) process is commonly used due to its effectiveness and the high quality of the end product. However, its main drawback is the significant loss of elements such as aluminum (Al) due to evaporation under the vacuum environment. Numerical coupled thermal-flow models were here developed to investigate the effects of scanning strategies on Al loss in a titanium alloy during EBCHM. The validation model was successful in comparison with previously published experimental data. The Al mass fraction results at the outlet of the water-cooled hearth were strongly influenced by changes in the applied scanning strategies. The results indicated that the Al mass fraction loss could be reduced by using the full-hearth scanning strategies.

Enhancement of photoconversion efficiency of ZnO nanorod-based dye-sensitized solar cells in presence of ZrO2 thin energy barrier.

In order to enhance the power conversion efficiency of ZnO nanorods-based dye-sensitized solar cells (DSSCs), ZrO2 thin energy barriers were formed on ZnO nanorods using a sol-gel method. In DSSCs, the short-circuit current was substantially increased, and the dark current was significantly reduced in the presence of the ZrO2 layer. Due to suppressed recombination in the presence of the ZrO2 layer, 81.3% increment of power conversion efficiency is achieved compared to those without ZrO2 layer.

Enhanced photocurrent generation of binary self-assembled monolayers of di-(3-aminopropyl)-viologen and methylviologen on indium tin oxide.

The binary self-assembled monolayers (SAMs) of di-(3-aminopropyl)-viologen (DAPV) and methylviologen (MV) molecules on indium tin oxide (ITO) were prepared by dipping the DAPV SAMs/ITO substrates into MV solution. The DAPV-MV SAM films were characterized by UV-vis. absorption spectroscopy, Rutherford backscattering spectroscopy, and cyclic voltammetry. Optical band gap, lowest unoccupied molecular orbital, and highest occupied molecular orbital of DAPV-MV SAMs were measured to be 1.6, -4.3, and -5.9 eV, respectively. We found that although DAPV SAMs have a quantum yield of 0.11%, the binary SAM films have a good quantum yield of 2.30%, which was 20 times higher than that of DAPV SAMs on ITO. This result may be due to the higher adsorption property of the binary SAMs for the light in visible range compared to that of DAPV SAMs. From this study, we demonstrated that the photocurrent generation systems with a high quantum yield can be obtained by the functional binary SAMs.