Tailoring Copper Chemical Status and Hydrophobicity of Biomimetic Photocatalytic Films for Carbon Dioxide Conversion.

Naturally hierarchical nanostructures of leaves were successfully replicated on thermally stable polyimide (PI) films to obtain biomimetic substrates for the grafting of p-type semiconductor, cuprous oxide (Cu2O). The chemical states of Cu2O and the hydrophobicity on the photocatalytic films were tunable by altering the process time of ion-exchange or chemical reduction. The obtained photocatalytic films showed activity to photocatalytically convert carbon dioxide (CO2) into carbon monoxide (CO) under visible light illumination. The yield of CO was initially improved with the increasing hydrophobicity on the film but then leveled off. The photocatalytic activity could be further improved by tailoring the amount or composition of copper oxides. An optimum ratio of Cu2O and moderate basicity on the surface, as well as more metallic Cu from the bulk, will achieve more efficient interfacial charge transfer, resulting in a higher CO production rate.

Sputtered anti-reflection layer on transparent polyimide - substrate improves adhesion strength to - copper layer: effects of layer thickness and sputtering power.

In order to shield the electronic circuits on a transparent polyimide (PI) substrate, an anti-reflection (AR) layer was deposited on a PI film via DC reactive magnetron sputtering. The effects of sputtering power and thickness of AR layer on the optical property and adhesion strength of the PI were investigated. The composition of the AR layer influences the bonding between layers. Sufficient thickness of the AR layer is essential to strengthen the adhesion between the PI and copper (Cu) layers. The sputtered AR layer on the PI also improves the barrier property for water vapor. The AR layer-sputtered PI substrates remain transparent and exhibit high peel strength to the Cu layer, suggesting their potential applications as reliable transparent substrates for modern electronic devices.

Anti-reflection Layer-Sputtered Transparent Polyimide Substrate with Reliable Adhesion Strength to the Copper Layer.

Parameters of DC-reactive magnetron sputtering are optimized to deposit anti-reflection (AR) layers on transparent polyimide (PI) substrates, followed by the deposition of the conductive copper layer, to fabricate practically reliable composite films as advanced flexible circuits. When the deposition thickness is controlled and the gas composition during sputtering is adjusted, the resultant AR layer-coated PI film exhibits low reflectance and reveals improved adhesion strength to the copper layer. The adhesion reliability tests confirm that the peel strength between the PI film and the deposited layers could be further improved after thermal processing due to the formation of a worm-like morphology for better mechanical interlocking with layers. The facile sputtering process successfully fabricates a reliable substrate material with low reflectance and sufficient adhesion strength to copper for application as flexible printed circuits.

Polyimide-derived graphite barrier layer adhered to seed crystals to improve the quality of grown silicon carbide.

A facial method was developed to in situ fabricate a graphite layer on a SiC seed crystal to reduce the formation of defects during the growth of SiC ingots. The formulated PI matrix combined with an appropriate coupling agent could strongly adhere to SiC and be transformed into protective layers for SiC seed crystals during SiC growth. The thermally conductive graphite layers on SiC effectively reduce the backside diffusion of Si, inhibit the loss of Si from seed crystals during high-temperature growing process, and consequently lead to fewer defects formed in the SiC ingot. The graphitization degree, chemical state, roughness and morphology of films were investigated in this work.

Bio-friendly titania-grafted chitosan film with biomimetic surface structure for photocatalytic application.

A series of biomimetic chitosan (CS) films grafted with titanium dioxide (TiO2) were successfully prepared for photocatalytic reduction of carbon dioxide (CO2). The replication of the hierarchical structure of natural leaves to the surface of CS was conducted by nanocasting technique. The presence of amine and hydroxyl groups on CS matrix was able to anchor TiO2 nanoparticles. The addition of cross-linking agent, glutaraldehyde, improved the denseness of CS matrix but affected the distribution of TiO2. The existence of biomimetic structures on films enhanced the hydrophobicity, thermal stability and CO2 adsorption. Moreover, the surface patterns influenced the optical absorption edge of TiO2-grafted films. Under the illumination of UVA (8-Watt) light source, the TiO2-grafted CS films were able to convert CO2 into carbon monoxide and trace amounts of methanol. The biofriendly CS-supported photocatalysts exhibited the potential for sustainable CO2 reduction for cleaner production of chemical fuels.

Anatase TiO2-Decorated Graphitic Carbon Nitride for Photocatalytic Conversion of Carbon Dioxide.

Three types of graphitic carbon nitride (gCN) nanosheets were derived from direct thermal condensation of urea, melamine, and dicyandiamide, respectively. As the sample (uCN) synthesized from urea exhibited porous morphology and highest surface area among other gCN, anatase TiO2 nanoparticles were then in-situ deposited on uCN via solvothermal process without further calcination. The resultant Ti/uCN_x samples remained with higher surface area and exhibited visible-light activity. The derived band structure of each sample also confirmed its ability to photoreduce CO2. XPS results revealed surface compositions of each sample. Those functional groups governed adsorption of reactant, interfacial interaction, electron transfer rate, and consequently influenced the yield of products. Carbon monoxide and methanol were detected from LED-lamp illuminated samples under appropriate moisture content. Samples with higher ratio of terminal amine groups produced more CO. The presence of hydroxyl groups promoted the initial conversion of methanol. The obtained Ti/uCN_0.5 and Ti/uCN_1.5 samples exhibited better quantum efficiency toward CO2 conversion and demonstrated stability to consistently produce CO under cycling photoreaction.

Flexible and transparent polyimide films containing two-dimensional alumina nanosheets templated by graphene oxide for improved barrier property.

Unique two-dimensional alumina nanosheets (Alns) using graphene oxide (GO) as templates are fabricated and successfully incorporated with organo-soluble polyimide (PI) to obtain highly transparent PI nanocomposite films with improved moisture barrier property. The effects of filler types and contents on water vapor transmission rate (WVTR) and transparency of PI are systematically studied. The hydroxyl groups on GO react with aluminum isopropoxide via sol-gel process to obtain alumina coverd-GO (Al-GO), and then thermal decomposition is applied to obtain Alns. Alns are the most efficient fillers among others to restrict the diffusion of water vapor within PI matrix and simultaneously maintain the transparency of PI. XRD pattern, TEM, and AFM images confirm the sheet-like morphology of Alns with ultrahigh aspect ratio. With only 0.01 wt % of Alns, the PI nanocomposite film exhibits the most significant reduction of 95% in WVTR as compared to that of pure PI film. Most importantly, the resultant PI/Alns-0.01 film exhibits excellent optical transparency and high mechanical strength and great thermal stability.

Flexible polyimide films hybrid with functionalized boron nitride and graphene oxide simultaneously to improve thermal conduction and dimensional stability.

Coupling agent-functionalized boron nitride (f-BN) and glycidyl methacrylate-grafted graphene (g-TrG) are simultaneously blended with polyimide (PI) to fabricate a flexible, electrically insulating and thermally conductive PI composite film. The silk-like g-TrG successfully fills in the gap between PI and f-BN to complete the thermal conduction network. In addition, the strong interaction between surface functional groups on f-BN and g-TrG contributes to the effective phonon transfer in the PI matrix. The thermal conductivity (TC) of the PI/f-BN composite films containing additional 1 wt % of g-TrG is at least doubled to the value of PI/f-BN and as high as 16 times to that of the pure PI. The hybrid film PI/f-BN-50/g-TrG-1 exhibits excellent flexibility, sufficient insulating property, the highest TC of 2.11 W/mK, and ultralow coefficient of thermal expansion of 11 ppm/K, which are perfect conditions for future flexible substrate materials requiring efficient heat dissipation.

NIST gold nanoparticle reference materials do not induce oxidative DNA damage.

One primary challenge in nanotoxicology studies is the lack of well-characterised nanoparticle reference materials which could be used as positive or negative nanoparticle controls. The National Institute of Standards and Technology (NIST) has developed three gold nanoparticle (AuNP) reference materials (10, 30 and 60 nm). The genotoxicity of these nanoparticles was tested using HepG2 cells and calf-thymus DNA. DNA damage was assessed based on the specific and sensitive measurement of four oxidatively-modified DNA lesions (8-hydroxy-2´-deoxyguanosine, 8-hydroxy-2´-deoxyadenosine, (5´S)-8,5´-cyclo-2´-deoxyadenosine and (5´R)-8,5´-cyclo-2´-deoxyadenosine) using liquid chromatography/tandem mass spectrometry. Significantly elevated, dose-dependent DNA damage was not detected at concentrations up to 0.2 µg/ml, and free radicals were not detected using electron paramagnetic resonance spectroscopy. These data suggest that the NIST AuNPs could potentially serve as suitable negative-control nanoparticle reference materials for in vitro and in vivo genotoxicity studies. NIST AuNPs thus hold substantial promise for improving the reproducibility and reliability of nanoparticle genotoxicity studies.