Digital light processing of SiC ceramic from allylhydridopolycarbosilane with limited acrylate monomers

Digital light processing of ceramic precursor was used to prepare SiC rich ceramic parts in this study. In order to achieve appropriate light curing rate, the ceramic precursor allylhydropolycarbosilane (LHBPCS) was mixed with acrylate monomers tripropylene glycol diacrylate and trimethylolpropane triacrylate. The content of acrylate monomers was optimized to increase the ceramic yield and reduce the shrinkage during pyrolysis. According to the results of thermogravimetric analysis and photolithography experiment, 15 wt% acrylate monomers was appropriate. 330 mJ/cm² UV irradiation dose was selected for every layer with a thickness of 25 μm, and green bodies with different shapes were successfully printed. During pyrolysis, these printed parts changed from transparent yellow to black accompanying uniform shrinkage. At 1000 °C, the shrinkage was 24.0–26.0%, and crack-free SiC rich ceramic parts with density of 2.11 g/cm³ and chemical formula of SiC_1.31O_0.26 were obtained.     

An approach to laminated flexible Dye sensitized solar cells

We have built TiO₂ Dye sensitized solar cells (DSSCs) that combined flexible TiO₂ photoanodes coated on ITO/PET substrates with a gel electrolyte based on PVDF-HFP-SiO₂ films. Titanium isopropoxide (TiP₄) was used as additive to TiO₂ nanoparticles for increasing power conversion efficiency in Dye sensitized solar cell electrodes prepared at low-temperature (130 °C). An efficiency η_AM1.5G = 3.55% on ITO/PET substrates is obtained at 48 mW/cm² illumination with a standard liquid electrolyte based on methoxypropionitrile. Among several solvents forming gels with PVDF-HFP-SiO₂, N-methyl (pyrrolidone) (NMP) was found to enable the most stable devices. A power conversion efficiency η_AM1.5G = 2% was obtained under 10 mW/cm² with flexible TiO₂-ITO-PET photoanodes and the PVDF-HFP-SiO₂ + NMP gel electrolyte.     

A novel negative photoinitiator-free photosensitive polyimide

A novel negative photoinitiator-free photosensitive polyimide (PFPS-PI) was synthesized through introducing the photosensitive 4,4-bis[(4-amino)thiophenyl] benzophenone (BATPB) into backbone chain and methyl acrylate group into side-chain of the polyimide, respectively. Photosensitive properties study revealed its good photolithographic properties, with a resolution about 5 μm and a sensitivity of 150 mJ/cm².     

Tungsten and nickel tungsten carbides as anode electrocatalysts

Tungsten and nickel tungsten carbides were evaluated as the anode catalysts of a polymer electrolyte fuel cell (PEFC). These catalysts were prepared by the temperature-programmed carburization of tungsten and nickel tungsten oxides from 573 to 873-1073 K in a stream of 20% CH₄/H₂ and kept at temperature for 3 h. The 30% tungsten and nickel tungsten carbides mixed with Ketjen carbon (KC) were evaluated by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and electrocatalytic activity (I-V performance) using a single cell. The W1023/KC catalyst achieved a power density of 6.4 mW/cm² (current density: 15.2 mA/cm²) which corresponded to 5.7% of that achieved by a commercial 20% Pt/C catalyst in a single cell (20% Pt/C: 111.7 mW/cm²) using our setup. From the XRD data, α-W₂C together with a small amount of WC was active during the anodic oxidation. The maximum power density of the 30 wt% 873 K-carburized NiW/KC was 8.2 mW/cm² at the current density of 19.0 mA/cm² which was 7.3% of the 20 wt% Pt/C.     

Investigation of 30-cell solid oxide electrolyzer stack modules for hydrogen production

The 30-cell nickel-yttria stabilized zirconia (Ni-YSZ) hydrogen electrode-supported planar solid oxide electrolyzer (SOE) stack modules were manufactured and tested at 800 °C in steam electrolysis mode for hydrogen production. The electrolysis efficiency of the stack modules was higher than 100% at a total steam and hydrogen flow of 2.1 sccm cm⁻², a H₂O/H₂ ratio of 80/20, and a current density of <0.2 A cm⁻². The electrolysis efficiency, current efficiency, and actual hydrogen production rate of the stack modules increased with increasing H₂O/H₂ ratio at a constant current density. However, the electrolysis and current efficiencies decreased steadily at high current densities. During hydrogen production, the stack modules were operated at 800 °C and a constant current density of 0.15 A cm⁻² for up to 1100 h. A steam conversion rate of 62% and current efficiency of 87.4% were obtained; the actual hydrogen production rate reached as high as 103.6 N L h⁻¹. Post-mortem analysis showed that delamination of the LSM–YSZ oxygen electrode mainly occurred in the steam and air inlet area of the 10×10 cm² cells.     

Application of a new model and measurement technique for dynamic shrinkage and conversion of multi-acrylates photopolymerized at different UV intensities

We have recently developed a new model and measurement technique for the dynamics of conversion and shrinkage during the photopolymerization of multi-acrylates. The model development and the application to different UV intensities were investigated in this paper. In this new model, instead of assigning the excess volume entirely as excess free volume, it is partitioned into both free and occupied volume components. The new measurement technique allowed us to collect real-time conversion and shrinkage data simultaneously and synchronously to verify our new model. When utilized on a broad range of incident UV intensities (3, 16 and 130 mW/cm²), there was considerable success for predicting conversion for all the cases, but the result is less satisfactory for shrinkage prediction at the highest UV intensity. Possible explanations of this discrepancy are discussed.     

Organelle-based biofuel cells: Immobilized mitochondria on carbon paper electrodes

This paper details the development of a mitochondria-based biofuel cell. We show that mitochondria can be immobilized at a carbon electrode surface and remain intact and viable. The electrode-bound mitochondria drive complete oxidation of pyruvate as shown by Carbon-13 NMR and serve as the anode of the biofuel cell where they convert the chemical energy in a biofuel (such as pyruvate) into electrical energy. These are the first organelle-based fuel cells. Researchers have previously used isolated enzymes and complete microbes for fuel cells, but this is the first evidence that organelles can support fuel cell-based energy conversion. These biofuel cells provide power densities of 0.203 ± 0.014 mW/cm², which is in between the latest immobilized enzyme-based biofuel cells and microbial biofuel cells, while providing the efficiency of microbial biofuel cells.     

Uniaxially oriented carbon monoliths as supercapacitor electrodes

Cylindrical carbon monoliths of 7 mm in diameter and certain heights (1, 2, 3, 4 and 5 mm) are studied as model electrodes for supercapacitors. The monoliths show a narrow microporous structure with average micropore size of 0.73 nm and specific surface area of 1086 m² g⁻¹. The monoliths show straight walls and channels, both arranged along the cylinder axis. The former account for a remarkable electrical conductivity (6.5 S cm⁻¹ at room temperature). The latter allow a rapid ionic transport between the electrolyte bulk and the carbon walls and account for a high specific capacitance at high current density. The cell capacitance and resistance increase linearly with the monolith height according to C = (1.78 ± 0.06)h and ESR = (0.08 ± 0.01)h + (1.67 ± 0.04), respectively. The contribution of the electrolyte resistance, monolith resistance and monolith/collector resistance to ESR is discussed. The cell response time or constant time increases with the monolith height but according to a power dependence, τ = (4.5 ± 0.2)h^{(1.61 ± 0.03)}. The carbon of the monoliths show in KOH electrolyte a specific capacitance of 150 F g⁻¹ and a capacitance per surface area of 14 μF cm⁻².     

Photosensitization of TiO2 nanorods with CdS quantum dots for photovoltaic devices

CdS quantum dots (QDs) coated TiO₂ nanorod arrays have been prepared via a two-step method. TiO₂ nanorod arrays were synthesized by a facile hydrothermal method, and CdS QDs were deposited on the nanorods by a sequential chemical bath deposition (S-CBD) technique. The surface morphology, structure, optical and photoelectrochemical behaviors of the core-shell nanorod array films are considered. A photocurrent of 2.5 mA/cm², an open circuit photovoltage of 1.10 V, and a conversion efficiency of 1.91% were obtained under an illumination of 100 mW/cm², when the CdS QDs deposited on TiO₂ nanorods film for about 7 cycles. The results demonstrate that the composite films are of excellence with respect to photovoltaic conversion.     

Effect of photosensitivity in acrylic photoreactive electrode pastes on line width uniformity for large‐sized plasma display panels

Ag electrodes with line width uniformity for large‐sized plasma display panels were successfully fabricated through a photolithographic process using photosensitive Ag pastes with optimized photosensitive properties. The photosensitivity of the Ag electrode pastes in the photolithographic process was investigated as a function of the types and contents of photoinitiators, the molecular weights and acid values of acrylic binders with carboxylic acid groups, and the process variables, such as the UV‐light intensity and dose, with a step tablet. This study revealed that the photoinitiator was a major parameter for the photosensitivity of the Ag electrode pastes. With the photosensitivity of the photosensitive Ag electrode pastes optimized by the study of the photoinitiator contents, Ag electrodes with line width uniformity were achieved with an HSP‐188 photoinitiator content of 15 wt % on the basis of the reactive monomers, regardless of the variation of the light dose from 250 to 350 mJ/cm² and intensity from 15 to 25 mW/cm². © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radical depletion model for intensity effects on photopolymerization

Photopolymerization behavior of suspensions based on monomers is determined by the curing kinetics of the monomer, the concentration of photoactives such as photoinitiator, inert dye or inhibitor, and the conditions of polymerization such as light intensity. We present a Radical depletion model, an extended Inhibitor exhaustion model, in terms of minimum light intensity that is required for initiation of the photopolymerization. The validity of this model was tested on a series of (meth)acrylate suspensions with varying the photoactives concentration in the intensity range ～8–40 mW/cm².     

Synthesis and characterization of novel photoconducting carbazole derivatives in main-chain polymers for photorefractive applications

We have prepared hole-transporting polymers that have carbazole and 3,3′-dicarbazole in the main chain by polycondensation based on Fridel-Craft reaction via cations generated by proton of p-toluene sulfonic acid catalyst. In the device, they display high diffraction efficiency at low external electric field. The DiCz composite had a high diffraction efficiency of 82.4% at 52 V/μm and a photorefractive response time constant of 1.18 s at an electric field of 50 V/μm and a writing intensity of 60 mW/cm². The samples have excellent properties with respect to optical quality and shelf-lifetime.     

The preparation of poly(glycidyl acrylate)-polypyrrole gel-electrolyte and its application in dye-sensitized solar cells

A microporous hybrid of poly(glycidyl acrylate)-polypyrrole (PGA-PPy) was synthesized by a two-step solution polymerization. Using this hybrid as polymer host, a gel-electrolyte with high conductivity of 12.83 mS cm⁻¹ was prepared. The researches by scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and cyclic voltammetry (CV) show that the microporous structure and functional groups for PGA allows the higher absorbency and good ionic salt tolerance for the electrolyte, the introduction of PPy causes a lower charge-transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction for the electrolyte. Based on the electrolyte, a dye-sensitized solar cell with a light-to-electrical energy conversion efficiency of 5.03% is achieved, under illumination with a simulated solar light of 100 mW cm⁻² (AM 1.5).     

Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI^® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25−3.25 (in the often employed expression ) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of k_t is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of k_t as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of k_t with conversion is more pronounced at increased chain lengths, with a strong decrease in k_t exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800.     

Fabrication of morphology controllable rutile TiO2 nanowire arrays by solvothermal route for dye-sensitized solar cells

Highly ordered, vertically oriented TiO₂ nanowire arrays (TNAs) are synthesized directly on transparent conducting substrate by solvothermal procedure without any template. The X-ray diffraction (XRD) pattern shows that TiO₂ array is in rutile phase growing along the (0 0 2) direction. The field-emission scanning electron microscopy (FE-SEM) images of the samples indicate that the TiO₂ array surface morphology and orientation are highly dependent on the synthesis conditions. In a typical condition of solvothermal at 180 °C for 2 h, the TNAs are composed of nanowires 10 ± 2 nm in width, and several nanowires bunch together to form a larger secondary structure of 60 ± 10 nm wide. Dye-sensitized solar cell (DSSC) assembled with the TNAs grown on the FTO glass as photoanode under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) achieves an overall photoelectric conversion efficiency of 1.64%.     

Development of alcohol/O2 biofuel cells using salt-extracted tetrabutylammonium bromide/Nafion membranes to immobilize dehydrogenase enzymes

Quaternary ammonium bromide salt-treated Nafion membranes provide an ideal environment for enzyme immobilization. Because these quaternary ammonium bromide salt-treated Nafion membranes retain the physical properties of Nafion and increase the mass transport of ions and neutral species through the membrane, they are also ideal for modifying electrodes. Therefore, high current density bioanodes are formed from poly(methylene green) (an electrocatalyst for NADH) modified electrodes that have been coated with a layer of tetrabutylammonium bromide salt-treated Nafion with dehydrogenase enzymes immobilized within the layer. Ethanol/O₂ biofuel cells employing these bioanodes have yielded power densities of 1.16 mW/cm² with a single-enzyme system (alcohol dehydrogenase) and 2.04 mW/cm² with a double-enzyme system (alcohol dehydrogenase and aldehyde dehydrogenase) in the polymer layer. Methanol/O₂ biofuel cells employing these bioanodes have yielded power densities of 1.55 mW/cm² and open circuit potentials of 0.71 V.     

D-A copolymers based on dithienosilole and phthalimide for photovoltaic materials

Two D-A copolymers containing dithienosilole (DTS) donor unit and phthalimide (Ph) acceptor unit, PDTSPh and PDTSBTPh, were synthesized by the Pd-catalyzed Stille-coupling method. The copolymers have a strong absorption ranging from 350 to 650 nm, exhibit good solubility and thermal stability. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of the copolymers determined by cyclic voltammetry were about −5.2 and −3.0 eV, respectively. The power conversion efficiency of the polymer solar cells based on PDTSBTPh:PC₇₀BM (1:2, w/w) reached 2.1% with open-circuit voltage of 0.83 V and a short-circuit current of 6.27 mA/cm², under the illumination of AM1.5, 100 mW/cm².     

Infrared and UV-vis spectra of phenoxonium cations produced during the oxidation of phenols with structures similar to vitamin E

Several phenols with structures similar to vitamin E were oxidised and the intermediate species produced were characterised by in situ infrared and UV-vis spectroscopies. The Fourier transform infrared (FTIR) measurements were performed by chemically oxidising the phenols with 2 mol equiv. of NO⁺SbF₆⁻ in CH₃CN and recording the spectra between 1900 and 1300 cm⁻¹ with an attenuated total reflectance (ATR) probe utilising a fiber conduit and a diamond composite sensor. The compounds that formed long-lived phenoxonium cations displayed two IR absorbances at 1665 (±15) cm⁻¹ and one at 1600 (±10) cm⁻¹ associated with the carbonyl, symmetric ring stretch and asymmetric ring stretch modes. The para-quinones are one of the long-term products of oxidation of the phenols, and displayed solution phase IR absorbances at 1650 (±10) cm⁻¹. In situ electrochemical UV-vis experiments performed during the oxidation of the phenols led to the detection of bands due to the phenoxonium cations at 295 (±5) and 440 (±15) nm and due to the para-quinones at 260 (±10) nm. The concentration of the substrate and the water content of the solvent had a major effect on the yields of the intermediates and products that were produced during the oxidation reactions.     

Development and characterization of a silicon-based micro direct methanol fuel cell

A silicon-based micro direct methanol fuel cell (μDMFC) for portable applications has been developed and its electrochemical characterization carried out in this study. Anode and cathode flowfields with channel and rib width of 750 μm and channel depth of 400 μm were fabricated on Si wafers using the microelectromechanical system (MEMS) technology. A membrane-electrode assembly (MEA) was specially fabricated to mitigate methanol crossover. This MEA features a modified anode backing structure in which a compact microporous layer is added to create an additional barrier to methanol transport thereby reducing the rate of methanol crossing over the polymer membrane. The cell with the active area of 1.625 cm² was assembled by sandwiching the MEA between two micro-fabricated Si wafers. Extensive cell polarization testing demonstrated a maximum power density of 50 mW/cm² using 2 M methanol feed at 60 °C. When the cell was operated at room temperature, the maximum power density was shown to be about 16 mW/cm² with both 2 and 4 M methanol feed. It was further found that the present μDMFC still produced reasonable performance under 8 M methanol solution at room temperature.     

Copolymerization and Dark Polymerization Studies for Photopolymerization of Novel Acrylic Monomers

The copolymerization behavior and the dark polymerization kinetics of highly reactive novel acrylic monomers were compared to traditional acrylate monomers. Copolymerization of thiol functionalities with novel acrylic monomers was characterized, and it was observed that the inclusion of secondary functionalities such as carbamates, carbonates, and cyclic carbonates, in acrylic monomers significantly alters the relative reactivity of the novel acrylates with thiols. While traditional aliphatic acrylates exhibited propagation to chain transfer ratios ranging between 0.8 (±0.1) and 1.5 (±0.2), the novel acrylates characterized by secondary functionalities exhibited much higher propagation to chain transfer ratios ranging from 2.8 (±0.2) to 4 (±0.2). In the dark polymerization studies, the kinetics of the novel acrylates were evaluated following cessation of the UV light. The novel acrylates exhibited extensive polymerization in the dark compared to most traditional acrylates and diacrylates. For instance, cyclic carbonate acrylate was observed to attain 35% additional conversion in the dark when the UV light was extinguished at 35% conversion, whereas traditional acrylates such as hexyl acrylate attained only 3% additional conversion when the UV light was extinguished at 35%, and a diacrylate such as HDDA attained 15% additional conversion when the UV light was extinguished at 40% conversion. Also, through choice of appropriate monomers, the dark polymerization studies were performed such that the polymerization rate was approximately the same at the point the light was extinguished for all these monomers. The copolymerization and dark polymerization studies support the hypothesis that the nature of the propagating species in the novel acrylates is altered as compared to traditional acrylic monomers and polymerizations.