Prediction of Lap Shear Strength and Impact Peel Strength of Epoxy Adhesive by Machine Learning Approach.

In this study, an artificial neural network (ANN), which is a machine learning (ML) method, is used to predict the adhesion strength of structural epoxy adhesives. The data sets were obtained by testing the lap shear strength at room temperature and the impact peel strength at -40 °C for specimens of various epoxy adhesive formulations. The linear correlation analysis showed that the content of the catalyst, flexibilizer, and the curing agent in the epoxy formulation exhibited the highest correlation with the lap shear strength. Using the analyzed data sets, we constructed an ANN model and optimized it with the selection set and training set divided from the data sets. The obtained root mean square error (RMSE) and R2 values confirmed that each model was a suitable predictive model. The change of the lap shear strength and impact peel strength was predicted according to the change in the content of components shown to have a high linear correlation with the lap shear strength and the impact peel strength. Consequently, the contents of the formulation components that resulted in the optimum adhesive strength of epoxy were obtained by our prediction model.

Surface modification of CuS counter electrodes by hydrohalic acid treatment for improving interfacial charge transfer in quantum-dot-sensitized solar cells.

High charge transfer resistance and low electrocatalytic activity of counter electrodes (CEs) are mainly responsible for the poor photovoltaic performance of quantum-dot-sensitized solar cells (QDSSCs). Herein, a novel strategy has been successfully introduced for the first time to improve the electrocatalytic activity and charge transfer properties of a copper sulfide (CuS) CE by modifying it with the addition of hydrohalic acids (HHA). Through the suitable surface modification of HHA-incorporated CuS CE, the charge transfer from the external circuit to the CE surface was effectively facilitated. The electrochemical analyses suggest that charge transfer resistance is sufficiently reduced at the CE/electrolyte interface by using the HHA-treated CuS CEs. This improvement is mainly attributed to the high electrocatalytic activity of the modified CEs for the reduction of the polysulfide redox couple electrolyte in QDSSCs. The device constructed with TiO2/CdS/CdSe/ZnS photoanodes and the hydrogen-fluoride-treated CuS (HFCuS) CE exhibits a power conversion efficiency of 4.25%, which is considerably higher than that of the device with the bare CuS CE (3.11%). These findings can facilitate the fabrication of highly efficient CEs for next-generation solar cells.

CAU-11-COOH with a V-Shaped Linker as a Catalyst for the Solvent-Free Synthesis of Cyclic Carbonates from CO2 and Epoxides.

An Al3+-based metal-organic framework (MOF), CAU-11-COOH, with a V-shaped ligand, DPSDA (3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride), was prepared using the solvothermal method, and was characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, and CO2 adsorption. The catalytic efficiency of CAU-11-COOH was investigated in the solvent-free cycloaddition of carbon dioxide with epoxides, which yielded five-membered cyclic carbonates under mild reaction conditions. CAU-11-COOH with a co-catalyst, tetrabutylammonium bromide (TBAB), gave higher than 98% yield of epichlorohydrin carbonate at 80 °C without a solvent. A plausible reaction mechanism in which the Lewis acidic metal center, an uncoordinated carboxyl group, and a nucleophilic bromide anion operate synergistically is proposed. The CAU-11-COOH catalysts were found to exhibit high thermal stability and could be reused more than four times without any significant reduction in activity.

Water-Tolerant DUT-Series Metal-Organic Frameworks: A Theoretical-Experimental Study for the Chemical Fixation of CO2 and Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone.

A series of highly thermally and hydrolytically stable porous solids with intriguing properties of zirconium- and hafnium-based metal-organic frameworks (MOFs) [Dresden University of Technology (DUT) series] was synthesized. The DUT MOFs were found to be effective catalysts for both epoxide-CO2 cycloaddition reactions and the catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL). In particular, 12-connected DUT-52(Zr) showed higher catalytic activity than eight- and six-connected catalysts in the synthesis of cyclic carbonates as well as in the production of γ-valerolactone (GVL). The secondary building unit connectivity, coexistence of a moderate number of acidic and basic sites, Brunauer-Emmett-Teller surface area, and combined effects of the pores of the MOFs seem to influence the catalytic activity. The reaction mechanism for the DUT-52(Zr)-mediated cycloaddition reaction of CO2 and the CTH reactions were investigated in detail by using periodic density functional theory calculations. To the best of our knowledge, this is the first detailed computational study for the formation of GVL from EL by using MOF as the catalyst. In addition, grand canonical Monte Carlo simulations predicted the strong interaction of CO2 molecules with the DUT-52(Zr) framework. Remarkably, the DUT-series catalysts possess extraordinary tolerance toward water. Further, DUT-52(Zr) is recyclable and is an efficient catalyst for cycloaddition and CTH reactions for at least five uses without obvious reductions in the activity or structural integrity.

Adenine-Based Zn(II)/Cd(II) Metal-Organic Frameworks as Efficient Heterogeneous Catalysts for Facile CO2 Fixation into Cyclic Carbonates: A DFT-Supported Study of the Reaction Mechanism.

We synthesized two new adenine-based Zn(II)/Cd(II) metal-organic frameworks (MOFs), namely, [Zn2(H2O)(stdb)2(5H-Ade)(9H-Ade)2]n (PNU-21) and [Cd2(Hstdb)(stdb)(8H-Ade)(Ade)]n (PNU-22), containing auxiliary dicarboxylate ligand (stdb = 4,4'-stilbenedicarboxylate). Both MOFs were characterized by multiple analytical techniques such as single-crystal X-ray diffraction (SXRD), powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscopy, as well as temperature program desorption and Brunauer-Emmett-Teller measurements. Both MOFs were structurally robust and possessed unsaturated Lewis acidic metal centers [Zn(II) and Cd(II)] and free basic N atoms of adenine molecules. They were used as heterogeneous catalysts for the fixation of CO2 into five-membered cyclic carbonates. Significant conversion of epichlorohydrin (ECH) was attained at a low CO2 pressure (0.4 MPa) and moderate catalyst (0.6 mol %)/cocatalyst (0.3 mol %) amounts, with over 99% selectivity toward the ECH carbonate. They showed comparable or even higher catalytic activity than other previously reported MOFs. Because of high thermal stability and robust architecture of PNU-21/PNU-22, both catalysts could be reused with simple separation up to five successive cycles without any considerable loss of their catalytic activity. Densely populated acidic and basic sites in both Zn(II)/Cd(II) MOFs facilitated the conversion of ECH to ECH carbonate in high yields. The reaction mechanism of the cycloaddition reaction between ECH and CO2 is described by possible intermediates, transition states, and pathways, from the density functional theory calculation in correlation with the SXRD structure of PNU-21.

Ionic-Liquid-Functionalized UiO-66 Framework: An Experimental and Theoretical Study on the Cycloaddition of CO2 and Epoxides.

A facile approach for modifying the UiO-66-NH2 metal-organic framework by incorporating imidazolium-based ionic liquids (ILs) to form bifunctional heterogeneous catalysts for the cycloaddition of epoxides to CO2 is reported. Methylimidazolium- and methylbenzimidazolium-based IL units (ILA and ILB, respectively) were introduced into the pore walls of the UiO-66-NH2 framework through a condensation reaction to generate ILA@U6N and ILB@U6N catalysts, respectively. The resultant heterogeneous catalysts, especially ILA@U6N, exhibited excellent CO2 adsorption capability, which makes them effective for cycloaddition reactions producing cyclic carbonates under mild reaction conditions in the absence of any cocatalyst or solvent. The significantly enhanced activity of ILA@U6N is attributed to the synergism between the coordinately unsaturated Lewis acidic Zr4+ centers and Br- ions in the bifunctional heterogeneous catalysts. The size effect of the ILs on coupling between the epoxide and CO2 was also studied for ILA@U6N and ILB@U6N. A periodic DFT study was performed to provide evidence of possible intermediates, transition states, and pathways, as well as to gain deeper insight into the mechanism of the ILA@U6N-catalyzed cycloaddition reaction between epichlorohydrin and CO2 .

Enhanced light absorption and charge recombination control in quantum dot sensitized solar cells using tin doped cadmium sulfide quantum dots.

The photovoltaic performance of quantum dot sensitized solar cells (QDSSCs) is limited due to charge recombination processes at the photoelectrode/electrolyte interfaces. We analyzed the effect of Sn4+ ion incorporation into CdS quantum dots (QDs) deposited onto TiO2 substrates in terms of enhancing light absorption and retarding electron-hole recombination at the TiO2/QDs/electrolyte interfaces. Sensitization involved depositing CdS QDs with different Sn4+ concentrations on the surface of TiO2 using a facile and cost-effective successive ionic layer adsorption and reaction (SILAR) method. Optimized photovoltaic performance of Sn-CdS sensitized QDSSCs was explored using CuS counter electrodes (CEs) and a polysulfide electrolyte. Structural and optical studies of the photoanodes revealed that the gaps between CdS nanoparticles were partially filled by Sn4+ ions, which enhanced the light absorption of the solar cell device. Electrochemical impedance spectroscopy (EIS) and open circuit voltage decay (OCVD) tests suggested that Sn4+ ions can remarkably retard electron-hole recombination at the interfaces, stimulate electron injection into semiconductor QD layers, and provide long-term electron lifetime to the cells. We found that solar cells based on CdS photoanodes doped with 10% Sn4+ ions exhibited a superior power conversion efficiency (PCE) of 3.22%, open circuit voltage (Voc) of 0.593 V, fill factor (FF) of 0.561, and short-circuit current density (Jsc) of 9.68 mA cm-2 under an air mass coefficient (AM) 1.5 G full sun illumination. These values were much higher than those of QDSSCs based on bare CdS photoanodes (PCE = 2.16%, Voc = 0.552 V, FF = 0.471, and Jsc = 8.31 mA cm-2).

Enhancement of Magnetoelectric Conversion Achieved by Optimization of Interfacial Adhesion Layer in Laminate Composites.

We report the effect of epoxy adhesion layers with different mechanical or physical property on a magnetoelectric (ME) composite laminate composed of FeBSi alloy (Metglas)/single-crystal Pb(Mg1/3Nb2/3)O3-Pb(Zr,Ti)O3/Metglas to achieve an improved ME conversion performance. Through theoretical simulation, it was revealed that the Young's modulus and the thickness of interfacial adhesives were major parameters that influence the conversion efficiency in ME composites. In the experimental evaluation, we utilized three epoxy materials with a distinct Young's modulus and adjusted the average thickness of the adhesion layers to optimize the ME conversion. The experimental results show that a thin epoxy layer with a high Young's modulus provided the best performance in the inorganic-based ME conversion process. By tailoring the interfacial adhesion property, the ME laminate generated a high conversion coefficient of 328.8 V/(cm Oe), with a mechanical quality factor of 132.0 at the resonance mode. Moreover, we demonstrated a highly sensitive alternating current magnetic field sensor that had a detection resolution below 10 pT. The optimization of the epoxy layers in the ME laminate composite provided significant enhancement of the ME response in a simple manner.

Interactions between brush-grafted nanoparticles within chemically identical homopolymers: the effect of brush polydispersity.

We systematically examined the polymer-mediated interparticle interactions between polymer-grafted nanoparticles (NPs) within chemically identical homopolymer matrices through experimental and computational efforts. In experiments, we prepared thermally stable gold NPs grafted with polystyrene (PS) or poly(methyl methacrylate) (PMMA), and they were mixed with corresponding homopolymers. The nanocomposites are well dispersed when the molecular weight ratio of free to grafted polymers, α, is small. For α above 10, NPs are partially aggregated or clumped within the polymer matrix. Such aggregation of NPs at large α has been understood as an autophobic dewetting behavior of free homopolymers on brushes. In order to theoretically investigate this phenomenon, we calculated two particle interaction using self-consistent field theory (SCFT) with our newly developed numerical scheme, adopting two-dimensional finite volume method (FVM) and multi-coordinate-system (MCS) scheme which makes use of the reflection symmetry between the two NPs. By calculating the polymer density profile and interparticle potential, we identified the effects of several parameters such as brush thickness, particle radius, α, brush chain polydispersity, and chain end mobility. It was found that increasing α is the most efficient method for promoting autophobic dewetting phenomenon, and the attraction keeps increasing up to α = 20. At small α values, high polydispersity in brush may completely nullify the autophobic dewetting, while at intermediate α values, its effect is still significant in that the interparticle attractions are heavily reduced. Our calculation also revealed that the grafting type is not a significant factor affecting the NP aggregation behavior. The simulation result qualitatively agrees with the dispersion/aggregation transition of NPs found in our experiments.

Domain swelling in ARB-type triblock copolymers via self-adjusting effective dispersity.

We investigated the domain spacing of an ordered structure formed by polydisperse ARB-type triblock copolymers (triBCPs) with random middle R blocks consisting of A and B monomers. ARB-type triBCPs were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the dispersities of all samples were controlled as narrow as ∼1.2. From the bulk and film morphologies, it was found that the domain swelling increases as the content of middle R blocks increases, which implies that the middle R block even with a small content plays a critical role in dilating the domain spacing. Since the random middle R blocks are energetically neutral, they can be segregated into either A or B blocks. The strong stretching theory (SST) suggests that the dispersities of the resulting constituent blocks are maximized to reduce the elastic energy associated with chain stretching, thereby leading to the dilation of domain spacing.

Molecular Tailoring of Poly(styrene-b-methyl methacrylate) Block Copolymer Toward Perpendicularly Oriented Nanodomains with Sub-10 nm Features.

We demonstrate a novel approach for fabricating vertically orientated, sub-10 nm, block copolymer (BCP) nanodomains on a substrate via molecular tailoring of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) BCP, one of the most widely used BCPs for nanopatterning. The idea is to incorporate a short middle block of self-attracting poly(methacrylic acid) (PMAA) between the PS and PMMA blocks, where the PMAA middle block promotes phase separation between PS and PMMA, while maintaining the domain orientation perpendicular to the substrate. The designed PS-b-PMAA-b-PMMA triblock copolymers, which were synthesized via well-controlled anionic polymerization, exhibited order-disorder transition temperatures higher than that of pristine PS-b-PMMA BCPs, indicating the promotion of phase separation by the middle PMAA block. For PS-b-PMAA-b-PMMA BCPs with total molecular weights of 21 and 18 kg/mol, the domain spacing corresponds to 19.3 and 16.7 nm, respectively, allowing us to fabricate sub-10 nm nanodomain structures. More importantly, it was demonstrated that the PMAA middle block, which has a higher surface energy than PS and PMMA, does not significantly alter lateral concentration fluctuations, which are responsible for phase-separation in the lateral direction. This enabled the vertical orientation of microdomains with sub-10 nm feature size on a PS-r-PMMA neutral surface without an additional neutral top layer. We anticipate that this approach provides an important platform for next-generation lithography and nanopatterning applications that require sub-10 nm features over large areas with simple process and reduced cost.

An activatable anticancer polymer-drug conjugate based on the self-immolative azobenzene motif.

Triggered cellular uptake of a synthetic graft copolymer carrying an anticancer drug is achieved through self-immolation of the side-chain azobenzene groups. In this concept, the conjugate is initially chemically neutral and does not possess cell-penetrating function. However, upon cleavage of the azobenzene moieties, a cascade process is initiated that ultimately reveals an ammonium cation in the vicinity of the polymer backbone. Hence, self-immolation results in the transformation of the neutral polymer chain into a polycation. This structural transformation allows the conjugate to be taken up by the cancer cells through favorable electrostatic interactions with the negatively charged phospholipid components of the cell membrane. Once inside the cells, the polymer releases covalently attached doxorubicin in a pristine form through a low pH activated release mechanism. The significance of this approach lies in the sensitivity of the azobenzene group to hypoxic conditions and to the enzyme azoreductase that is secreted by the microbial flora of the human colon and suggests a pathway to targeted drug delivery applications under these conditions.

Three-Dimensional Multilayered Nanostructures from Crosslinkable Block Copolymers.

Block copolymer (BCP) lithography has generally been synonymous to one- or two-dimensional single layered lithographic templates as a means to fabricate simple nanoscaled structures. Recently, the rapidly increasing demand for complex nanostructures and the corresponding evolution in BCP lithography have led to three-dimensional (3D) BCP nanostructures, which can be fabricated in various ways such as directed self-assembly or stacking of cross-linked BCP patterns. This review covers the recent advances in the 3D multilayered structures from cross-linkable BCPs, which provide an easy and robust means for integrating various BCP structures into one scaffold. In this case, wetting-optimized adjustment of BCP microdomains at the layer interface plays a critical role in the formation of well-defined 3D multilayer nanostructures.

Combined epitaxial self-assembly of block copolymer lamellae on a hexagonal pre-pattern within microgrooves.

The directed self-assembly (DSA) of block copolymers (BCPs) has emerged as an alternative method to replace or complement conventional photolithography as a result of the approximately 10 nm scale of microdomain ordering, the variety of microstructures that can be obtained and its compatibility with current lithographic processes. In DSA, BCP microdomains are controlled via guide patterns and two main techniques are popular: graphoepitaxy and chemoepitaxy assembly. We have demonstrated a simple and feasible technology for a DSA process by combining graphoepitaxy with "inexpensive" chemoepitaxial assembly to improve the alignment of the lamellar microdomains. For chemoepitaxial assembly, the hexagonal surface patterns from cross-linkable, cylinder-forming BCP were used to guide the graphoepitaxial assembly of the overlying BCP lamellar film. When the guiding patterns were prepared on the hexagonal patterns, it was found that the degree of lamellar alignment was significantly improved compared with the lamellar alignment on the homogeneous neutral layers. Simulation results suggested that the underlying hexagonal pattern can assist the lamellar alignment by reducing the large number of orientation states of the lamellar layers. This strategy is applicable to various nanofabrication processes that require a high degree of fidelity in controlling the nanopatterns over large areas with reduced costs.

Blue and blue-green light-emitting cationic iridium complexes: synthesis, characterization, and optoelectronic properties.

Two new cationic iridium complexes, [Ir(ppy)2(phpzpy)]PF6 (complex 1) and [Ir(dfppy)2(phpzpy)]PF6 (complex 2), bearing a 2-(3-phenyl-1H-pyrazol-1-yl)pyridine (phpzpy) ancillary ligand and either 2-phenylpyridine (Hppy) or 2-(2,4-difluorophenyl)pyridine (Hdfppy) cyclometalating ligands, were synthesized and fully characterized. The photophysical and electrochemical properties of these complexes were investigated by means of UV-visible spectroscopy, emission spectroscopy, and cyclic voltammetry. Density functional theory (DFT) and time dependent DFT (TD-DFT) calculations were performed to simulate and study the photophysical and electrochemical properties of both complexes. Light-emitting electrochemical cells (LECs) were fabricated by incorporating complexes 1 and 2, which respectively exhibit blue-green (488 and 516 nm) and blue (463 and 491 nm) emission colors, achieved through the meticulous design of the ancillary ligand. The luminance and current efficiency measurements recorded for the LEC based on complex 1 were 1246 cd m(-2) and 0.46 cd A(-1), respectively, and were higher than those measured for complex 2 because of the superior balanced carrier injection and recombination properties of the former.

Perpendicularly Oriented Block Copolymer Thin Films Induced by Neutral Star Copolymer Nanoparticles.

By introducing neutral star copolymers consisting of poly(styrene-r-methyl methacrylate) (PS-r-PMMA) arms, a perpendicular orientation of PS-b-PMMA microdomains in thin films could be achieved without any surface treatment. The star copolymers were synthesized by arm-first method in which short chain arms are cross-linked by employing a multifunctional coupling reagent via atom transfer radical polymerization. To find the optimal neutral composition for the perpendicular orientation, we varied the composition of MMA in PS-r-PMMA arms from 40 mol % to 80 mol %. It was found that the star copolymer having an overall PS and PMMA composition of 59:41 exhibits the well-ordered perpendicular orientation of lamellar structures after thermal annealing. Furthermore, we also prepared the deuterated star copolymers to trace them within PS-b-PMMA films along vertical direction by neutron reflectivity. In this case, it was observed that star copolymers were mainly located at the top surface and bottom interface of the films, thereby effectively neutralizing the surface/interfacial energy differences.

Single Step Process for Self-Assembled Block Copolymer Patterns via in Situ Annealing during Spin-Casting.

We demonstrated a simple and time-efficient processing method for facilitating a microphase separation of block copolymers (BCPs) based on a single step of spin-casting with low volatile solvent and in situ annealing. Well-ordered lamellar patterns of poly(styrene-b-methyl methacrylate) BCP films having wide range of molecular weights (51-235 kg/mol) were fabricated by a single 3 min process of spin-casting, even without the conventional pretreatment of substrate neutralization. The formation of this well-ordered lamellar structure is attributed to a synergetic effect between slow solvent evaporation and thermal energy that may provide an efficient cooling profile for the BCP film during the spin-casting process.

Constructive effects of long alkyl chains on the electroluminescent properties of cationic iridium complex-based light-emitting electrochemical cells.

A series of cationic iridium complexes (1-6) were synthesized using alkylated imidazole-based ancillary ligands, and the photophysical and electrochemical properties of these complexes were subsequently evaluated. Light-emitting electrochemical cells (LECs) were fabricated from these complexes, and the effects of the alkyl chain length on the electroluminescent properties of the devices were investigated. The LECs based on these complexes resulted in yellow emission (complexes 1, 3, and 5) and green emission (complexes 2, 4, and 6) with Commission Internationale de L'Eclairage (CIE) coordinates of (0.49, 0.50) and (0.33, 0.59), respectively. Our results indicate that the luminance and efficiency of the LECs can consistently be enhanced by increasing the alkyl chain length of the iridium complexes as a result of suppressed intermolecular interaction and self-quenching. Subsequently, a high luminance of 7309 cd m(-2) and current efficiency of 3.85 cd A(-1) were achieved for the LECs based on complex 5.

Fabrication of nanostructured ZnO film as a hole-conducting layer of organic photovoltaic cell.

We have investigated the effect of fibrous nanostructured ZnO film as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the concentration of zinc acetate dihydrate, the changes of performance characteristics were evaluated. Fibrous nanostructured ZnO film was prepared by sol-gel process and annealed on a hot plate. As the concentration of zinc acetate dihydrate increased, ZnO fibrous nanostructure grew from 300 to 600 nm. The obtained ZnO nanostructured fibrous films have taken the shape of a maze-like structure and were characterized by UV-visible absorption, scanning electron microscopy, and X-ray diffraction techniques. The intensity of absorption bands in the ultraviolet region was increased with increasing precursor concentration. The X-ray diffraction studies show that the ZnO fibrous nanostructures became strongly (002)-oriented with increasing concentration of precursor. The bulk heterojunction photovoltaic cells were fabricated using poly(3-hexylthiophene-2,5-diyl) and indene-C60 bisadduct as active layer, and their electrical properties were investigated. The external quantum efficiency of the fabricated device increased with increasing precursor concentration.

Effects of pentacene-doped PEDOT:PSS as a hole-conducting layer on the performance characteristics of polymer photovoltaic cells.

We have investigated the effect of pentacene-doped poly(3,4-ethylenedioxythiophene:poly(4-styrenesulfonate) [PEDOT:PSS] films as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the amount of pentacene and the annealing temperature of pentacene-doped PEDOT:PSS layer, the changes of performance characteristics were evaluated. Pentacene-doped PEDOT:PSS thin films were prepared by dissolving pentacene in 1-methyl-2-pyrrolidinone solvent and mixing with PEDOT:PSS. As the amount of pentacene in the PEDOT:PSS solution was increased, UV-visible transmittance also increased dramatically. By increasing the amount of pentacene in PEDOT:PSS films, dramatic decreases in both the work function and surface resistance were observed. However, the work function and surface resistance began to sharply increase above the doping amount of pentacene at 7.7 and 9.9 mg, respectively. As the annealing temperature was increased, the surface roughness of pentacene-doped PEDOT:PSS films also increased, leading to the formation of PEDOT:PSS aggregates. The films of pentacene-doped PEDOT:PSS were characterized by AFM, SEM, UV-visible transmittance, surface analyzer, surface resistance, and photovoltaic response analysis.