Needle-shaped Crystals Research Articles

Electrochemical Deposition of Materials for Biomedical Applications

Electrochemical methods have been developed for the deposition of biopolymer films containing hydroxyapatite, and other bioceramics, such as titania, silica and bioglass. Different electrochemical methods have been utilized for the deposition of natural biopolymers, such as chitosan, polyacrylic acid and hyaluronate. Chitosan was protonated and dissolved in acidic solutions and then deposited cathodically. In this approach the charge neutralization of cationic chitosan in the high pH region at the electrode surface resulted in the precipitation of insoluble chitosan. Electrodeposition of alginic acid was performed from sodium alginate solutions. In this method the pH decrease at the anode surface resulted in the charge neutralization of alginate macromolecules and the fabrication of alginic acid films on anodic substrates. A similar approach has been utilized for the deposition of hyaluronic acid from the sodium hyaluronate solutions. It was demonstrated that cathodic and anodic deposition methods can be used for the deposition of other biopolymers. Nanoparticles of hydroxyapatite were prepared by a chemical precipitation method. Precipitation was performed at 70 °C by the slow addition of a 0.6 M ammonium phosphate solution into a 1.0 M calcium nitrate solution. The pH of the solutions was adjusted to 11 by NH4OH. Stirring was performed during 8 h at 70 °C and then 24 h at room temperature. The precipitate was washed with water and finally with ethanol. The average length of the needle-shape HA crystals, prepared by this method, was about 150 nm and the average aspect ratio was 8. The composite films containing HA nanoparticles in chitosan, alginic acid and hyaluronic acid matrix were prepared on stainless steel, Ti and NiTi alloy substrates. The results of thermogravimetric analysis showed that hydroxyapatite content in the polymer matrix was varied in the range of 35-80 wt% by variation of hydroxyapatite or polymer concentration in the solutions. The deposition yield was studied at different deposition conditions. It was shown that film thickness can be varied in the range of 0.1-200 microns by variation of the deposition time in the range of 1-10 min and deposition voltage in the range of 10-60 V. The composite films were prepared as monolayers or multilayers containing hydroxyapatite-polymer layers, separated by the layers of pure polymer. The co-deposition of inorganic materials with biopolymers resulted in the fabrication of novel composite materials containing bioactive glass and other bioactive materials, such as silica and titania in a polymer matrix. Electrochemical techniques have been also applied for the fabrication of materials of graded composition (FGM) containing biopolymers, hydroxyapaite and other bioceramics and bioglass. Electrochemical impedance spectroscopy and potentiodynamic polarization studies showed that the composite coatings provided corrosion protection of the metallic substrates in simulated body fluid solutions. The use of biopolymers enabled the room temperature processing of the coatings, eliminating the problems related to the sintering of hydroxyapatite and other bioceramics. Moreover, the method enabled the incorporation of drugs and proteins in the composite material. Electrochemical strategies have been developed for the deposition of composite films containing heparin and albumin in a biopolymer matrix. The room temperature processing offers a possibility of co-deposition of other functional materials and fabrication of advanced nanocomposite coatings for biomedical applications. New deposition methods were developed for cathodic deposition of chiral biopolymers, such as poly-l-lysine and polyl-ornithine. As an extension of these investigations, the composite films, containing HA nanoparticles and other functional biomaterials in the matrix of chiral biopolymers were obtained and investigated. Further development of new deposition methods resulted in the development of electrophoretic strategies and deposition mechanisms for the deposition of linear polyethylenimine, polypyrrole, polyetheretherketone, polyacrylic acid. Fundamental mechanisms were developed for the co-deposition of enzymes and proteins with various biopolymers. We discovered a possibility of electrophoretic co-deposition of halloysite nanotubes with cationic and anionic biopolymers, such as chitosan, poly-l-lysine and polyl-ornithine, alginic acid, hyaluronic acid, polyacrylic acid. The halloysite nanotubes can be loaded with drugs and antimicrobial agents for the controlled release. The new composite materials are prtomising for applications in biomedical implants and biosensors. We investigated functional properties of new materials, fundamental deposition mechanisms and kinetics of deposition.

Influence factors on activity of Ru–Zn catalysts in selective hydrogenation of benzene

Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selective hydrogenation of benzene were explored. A series of Ru–Zn catalysts with different Zn contents and ZnO morphologies were prepared by changing the amount of NaOH in the co-precipitation process. The catalysts were characterized by N2 physisorption, X-ray powder diffraction (XRD), inductively coupled plasma optical emission spectrometer (ICP-OES), scanning electron microscope (SEM), temperature-programmed reduction (H2-TPR) and Malvern laser particle size analyzer. It is found that with increasing the amount of NaOH, the Zn content first increased then decreased, and the ZnO crystals changed from relatively thicker pyramidal-shaped crystals to slimmer needle-shaped crystals. The catalyst had the highest Zn content (22.1%) and strongest interaction between ZnO crystals and Ru particles at pH10.6 of the solution after reduction. As a result, it had the lowest activity. The activity of Ru–Zn catalysts is affected by both the Zn content and the interaction between ZnO crystals and Ru particles. The effect of reduction time was also investigated. Prolonging the reduction time caused no significant growth of ZnO crystals but the aggregation of catalyst particles and growth of Ru nanocrystals, thus resulting in the decrease of catalytic activity.

The effect of 4-hexylresorcinol on xenograft degradation in a rat calvarial defect model

BackgroundThe objective of this study was to evaluate xenograft degradation velocity when treated with 4-hexylresorcinol (4HR).MethodsThe scapula of a cow was purchased from a local grocery, and discs (diameter 8 mm, thickness 1 mm) were prepared by trephine bur. Discs treated with 4HR were used as the experimental group. Untreated discs were used as the control. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), antibacterial test, endotoxin test, and scanning electron microscopy (SEM) were performed on the discs. In vivo degradation was evaluated by the rat calvarial defect model.ResultsThe XRD and FT-IR results demonstrated successful incorporation of 4HR into the bovine bone. The experimental disc showed antibacterial properties. The endotoxin test yielded results below the level of endotoxin contamination. In the SEM exam, the surface of the experimental group showed needle-shaped crystal and spreading of RAW264.7 cells. In the animal experiments, the amount of residual graft was significantly smaller in the experimental group compared to the control group (P = 0.003).ConclusionsIn this study, 4HR was successfully incorporated into bovine bone, and 4HR-incorporated bovine bone had antibacterial properties. In vivo experiments demonstrated that 4HR-incorporated bovine bone showed more rapid degradation than untreated bovine bone.

Synthesis of TiO<sub>2</sub>-Modified Hydroxyapatite with Various Morphology by Urea-Assisted Hydrothermal Method

In this study, we synthesized the TiO2-modified hydroxyapatite (HAp) with various morphologies by hydrothermal treatment using urea decomposition, at 160 oC for 6 h. After hydrothermal treatment, carbonate-substituted HAp and TiO2 (anatase) phases were formed in products using 1.0-0.1 M urea solution. The morphology of synthesized HAp changed from small plate-shaped to long needle-shaped crystals with decreasing the urea concentration. The photocatalytic property for samples was investigated by decoloration test using 25 ppm methylene blue solution. In comparison with HAp samples without TiO2, the TiO2-modified HAp clearly showed the photocatalytic decomposition of methylene blue by UV irradiation.

Crystal growth by Bridgman and Czochralski method of the ferromagnetic quantum critical material YbNi4P2

The tetragonal YbNi4P2 is one of the rare examples of compounds that allow the investigation of a ferromagnetic quantum critical point. We report in detail on two different methods which have been used to grow YbNi4P2 single crystals from a self-flux. The first, a modified Bridgman method, using a closed crucible system yields needle-shaped single crystals oriented along the [001]-direction. The second method, the Czochralski growth from a levitating melt, yields large single crystals which can be cut in any desired orientation. With this crucible-free method, samples without flux inclusions and a resistivity ratio at 1.8K of RR1.8K=17 have been grown.

Trans-free margarine fat produced using enzymatic interesterification of rice bran oil and hard palm stearin.

Trans-free interesterified fats were prepared from blends of hard palm stearin (hPS) and rice bran oil (RBO) at 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, and 80:20 weight % using immobilized Mucor miehei lipase at 60°C for 6 h with a mixing speed of 300 rpm. Physical properties and crystallization and melting behaviors of interesterified blends were investigated and compared with commercial margarine fats. Lipase-catalyzed interesterification modified triacylglycerol compositions and physical and thermal properties of hPS:RBO blends. Slip melting point and solid fat contents (SFC) of all blends decreased after interesterification. Small, mostly β' form, needle-shaped crystals, desirable for margarines were observed in interesterified fats. Interesterified blend 40:60 exhibited an SFC profile and crystallization and melting characteristics most similar to commercial margarine fats and also had small needle-like β' crystals. Interesterified blend 40:60 was suitable for use as a transfree margarine fat.

Tophaceous gout in thalassemia intermedia: a rare association.

A 32-year-old male presented with progressive swelling of fingers of both hands and joint pains. On physical examination, the patient had severe pallor, frontal bossing, zygomatic prominence, malocclusion of teeth and tophaceous deposits at knuckles and pinna (Fig. 1a). There was mild hepatomegaly and massive splenomegaly. On investigation, his hemoglobin was 6.1 g/dl (normal levels 13–17 g/dl), and he had microcytic normochromic anemia. He also had elevated uric acid levels of 14 mg/dl (normal levels 3.5–7 mg/dl) suggesting a hypermetabolic state. Chest and skull radiograph showed extramedullary hematopoiesis; skull radiograph revealed sun-ray appearance. Plain radiograph of the hands showed erosion of few phalanges, soft tissue swelling and ‘punched-out’ lytic lesions with sclerotic margins and overhanging bony edges (Martel's sign) [1] (Fig. 1b). Joint fluid aspiration revealed needle-shaped birefringent monosodium urate crystals. A genotypic diagnosis of double heterozygous thalassemia with hemoglobin E trait and phenotypic diagnosis of thalassemia intermedia with secondary chronic tophaceous gout was made. Crystal proven gout in a patient with thalassemia intermedia is a rare but important association. Figure 1: (a) Tophaceous deposits at pinna and (b) Martel's sign.

Effect of superplasticisers on the hydration process, products and microstructure of tricalcium aluminate paste in the presence of gypsum

The effects of three commonly used superplasticisers (SPs) – sulfonated naphthalene formaldehyde (SNF), sulfonated acetone formaldehyde (SAF) and polycarboxylates (PCB) – on the hydration process, products and microstructure of tricalcium aluminate (C3A) pastes in the presence of gypsum were systematically investigated using isothermal calorimetry, x-ray diffraction, environmental scanning electron microscopy, infrared spectroscopy and magic angle spinning–nuclear magnetic resonance spectroscopy. The results show that the hydration reaction rate of C3A paste at the initial stage (0–2 h) was promoted by the incorporation of SPs, especially in the C3A–SNF paste. Hydration was rapidly reduced at the early stage (2–12 h), but an acceleration in C3A–SNF/PCB pastes occurred again at the late stage. The morphology of the C3A–SNF/SAF paste changed from thin needle-shaped crystals at the initial stages to thick and coarse rod-like crystals at late stages. In the C3A–PCB paste, very few crystals occurred at an early age, while a large amount of prismatic crystals were observed at the later age. Chemical environment studies revealed that the SPs did not visibly change the position or shape of the characteristic bands of aluminates, but only influenced their relative intensities. A predominant resonance, assigned to six-coordinated aluminium as [AlO6] type, was observed for all the pastes with and without SP. The interaction mechanism between SP and C3A was also explored.

Mechanical properties of zirconia reinforced lithium silicate glass-ceramic

ObjectiveThe aim of this study was to assess the mechanical properties of recently introduced zirconia reinforced lithium silicate glass-ceramic. MethodsTwo types of CAD/CAM glass-ceramics (Vita Suprinity (VS); zirconia reinforced lithium silicate and IPS e.max CAD (IC); lithium disilicate) were used. Fracture toughness, flexural strength, elastic modulus, hardness, brittleness index, and microstructures were evaluated. Data were analyzed using independent t tests. Weibull analysis of flexural strength data was also performed. ResultsVS had significantly higher fracture toughness (2.31±0.17MPam0.5), flexural strength (443.63±38.90MPa), elastic modulus (70.44±1.97GPa), and hardness (6.53±0.49GPa) than IC (P<0.001). On the other hand, VS glass-ceramic revealed significantly a higher brittleness index (2.84±0.26μm−1/2) (lower machinability) than IC glass-ceramic (P<0.05). VS demonstrated a homogeneous fine crystalline structure while, IC revealed a structure with needle-shaped fine-grained crystals embedded in a glassy matrix. The VS glass-ceramic revealed a lower probability of failure and a higher strength than IC glass-ceramic according to Weibull analysis. SignificanceThe VS zirconia reinforced lithium silicate glass-ceramic revealed higher mechanical properties compared with IC lithium disilicate glass-ceramic.

Model for Interpreting Surface Crystallization Using Quartz Crystal Microbalance: Theory and Experiments.

Surface crystallization of calcium sulfate was investigated using a dissipation crystal quartz microbalance (QCM-D) together with microscopy to understand the mechanical property changes occurring during the growth process. The use of optical microscopy and SEM revealed that needle-shaped crystals grow as clusters on the QCM sensor's surface, not in uniform layers. As crystallization growth progressed, QCM-D revealed inversions between negative and positive frequency shifts. This behavior, a function of the growth of crystals in clusters, is not adequately predicted by existing models. As such, a new mass-to-frequency conversion model is proposed herein to explain the observed frequency inversions. This model is derived from a lumped element approach with point-contact loading and Mason equivalent circuit theory. Critically, the physical phenomena occurring form the basis of the model, particularly addressing the three sources of impedance. When a crystal nucleates and grows, its inertial impedance is considered along with a Kelvin-Voigt link with a hydration layer. A comparison between the proposed model and experimental data, of both frequency and dissipation data for the first four harmonics, shows good agreement for the supersaturations (S = C/C*) of S = 3.75, S = 3.48, and S = 3.22. Additionally, significant improvements over existing models for the case of surface crystallization are observed. The proposed model was therefore able to explain that frequency inversions are caused by a shift from inertia-dominated to elastic-dominated impedance, occurring as a result of crystal growth. Using the nucleation induction time and nucleation rates, determined with imaging, an additional understanding of the crystals' mechanical properties (stiffness and dampening) was obtained.

Mineralogy and Microbial Diversity of the Microbialites in the Hypersaline Storr's Lake, the Bahamas.

Microbialites found in the low-light-intensity, hypersaline waters of Storr's Lake (SL), San Salvador Island, the Bahamas, were investigated with respect to their morphology, mineralogy, and microbial diversity. Previously described microbialite morphologies, as well as a newly identified "multi-cuspate" morphology, were observed at various depths. Electron microscopy analysis revealed the presence of angular, blocky, and needle-shaped crystals with mineralized cyanobacterial filaments and remains of exopolymeric substances. X-ray diffraction studies confirmed the presence of both Mg-calcite and aragonite in the plateau-mushroom and pinnacle mound microbialites, whereas only Mg-calcite was identified in the other microbialite morphotypes. A comprehensive molecular analysis using barcoded pyrosequencing of five different microbial mat communities identified at least 12 dominant bacterial phyla. Cyanobacteria were generally low in abundance and ranged from ∼0.01% in the deeper pinnacle mounds to ∼3.2% in the shallow calcareous knobs. Other photosynthetic members included green nonsulfur bacteria of the phylum Chloroflexi and purple sulfur bacteria of the class Gammaproteobacteria. All mat types contained significant amounts of sulfate-reducing and dehalogenating bacteria. The low light intensity reaching the deeper microbialites, the lack of dominant cyanobacteria, and the abundance of sulfate reducers and Chloroflexi collectively suggest that sulfate reduction and anoxygenic photosynthetic processes influence the carbonate biomineralization process in these systems.

Nature of the of polymorphism of salt crystals in the aspect of arborization diagnostic method

Background. A method of medical diagnostics, called arborization (or ferning), is widely used. Despite this, nature of arborization of biological liquids remains unclear. As it is not enough, we tried to reveal the physical basis of arborization. Objective. To make known the physical and chemical bases of salts polymorphism, including arborization. Results. It was found that a crystal shapes that had been formed upon evaporation of saline solutions depends on the value of the electric potential of such solutions also on the value of the electric charge of the surface on which crystals are formed. It has been particularly found that the evaporation of solutions with positive electric potential is accompanied by the formation of cubic crystals and the evaporation of solutions with negative electric potential is accompanied by the formation of needle-like crystals. It was shown that the cubic crystals of NaCl, the basic salt component of human biological fluids, are formed on the positively charged surface of activated carbon. It was also shown that the needle-shaped crystals of NaCl are formed on the negatively charged surface of silica gel. Conclusion. Various forms of the crystals formed during evaporation of biological liquids of women, reflect the cyclic change in electric potential in such liquids during the menstrual cycle.

Gamma radiation induces hydrogen absorption by copper in water.

One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

Quantifying the effect of fillers on the breakage behaviour of needle-shaped particles

Understanding the relationship between the applied stress and the behaviour of packings of breakable granular particles is required in many chemical engineering applications. A pharmaceutical tablet is an example where a composite packing (a packing containing a mixture of several kinds of particles) is compacted in the process of tablet formation. In this work, the unidirectional compaction and the breakage processes in composite packings formed from a mixture of breakable needle-shaped crystals and elastic spherical filler particles were studied using a Discrete Element Method (DEM) simulation. The evolution of crystal size distribution and contacts topology with the increasing stress was computed for different relative size, volume fraction and elasticity of filler particles inside the packing. We show that crystals breakability in a packing is directly related to the number of contacts among particles and that it can be significantly influenced by an appropriate choice of added filler particles. The results can be used for the development of mathematical models that describe the pharmaceutical tablet production and other processes involving composite packings of fragile particles.

Furfurylated wood: impact onPostia placentagene expression and oxalate crystal formation

AbstractModified wood can provide protection against a range of wood deteriorating organisms. Several hypotheses have been put forward regarding the protection mechanisms against wood decaying fungi including fungal enzyme inefficiency due to non-recognition, lower micropore size, and insufficient wood moisture content. The aim of this study was to obtain new insight into the protection manner of furfuryl alcohol (FA) modified Scots pine sapwood (WFA), and to examine biochemical mechanisms and adaptive changes in gene expression utilised byPostia placentaduring early colonisation of WFA. Samples were harvested after 2, 4, and 8 weeks of incubation. After 8 weeks, the mass loss (0.1%) and wood moisture content (21.0%) was lower inWFA, than in non-modified Scots pine sapwood samples (W), 26.1% and 46.1%, respectively. Microscopy revealed needle-shaped calcium oxalate crystals, at all harvesting points, most prominently present after 4 and 8 weeks, and only in the WFAsamples. Among the findings based on gene profiles were indications of a possible shift toward increased expression, or at least no down regulation, of genes related to oxidative metabolism and concomitant reduction of several genes related to the breakdown of polysaccharides in WFAcompared to W.

Synthesis of morphologically controlled hydroxyapatite from fish bone by urea-assisted hydrothermal treatment and its Sr2 + sorption capacity

Needle- and sponge-shaped hydroxyapatite (HAp) particles were synthesized from calcined tuna fish bone (Tn1000) and commercially available HAp reagent (ChemHAP) by a urea-assisted hydrothermal treatment using 0.1–1.0M urea solution at 160°C for 3h. The Sr2+ sorption capacity of the synthesized HAp was also investigated using 0–50mM Sr2+ solution at 25°C for 72h to evaluate its performance as a sorbent for environmental remediation. Sponge-shaped HAp was formed under hydrothermal conditions with a urea concentration of 1.0M. With decreasing urea concentration, the morphology of HAp changed from sponge-shaped to needle-shaped crystals, regardless of the starting material. Some calcium carbonate and/or β-tricalcium phosphate impurities were formed from Tn1000 at 0.1–0.5M urea concentration. The Sr2+ sorption mechanism of the synthesized HAp was estimated using Ca ion-exchange reaction and precipitation of SrCO3. The sponge-shaped HAp crystals, which had high specific surface area and CO32− content, exhibited a large ion-exchange capacity with Sr2+. In contrast, the ion-exchange ratio of needle-shaped HAp dramatically decreased with increasing initial Sr concentration. No clear difference in Sr2+ sorption behaviour caused by the choice of HAp synthesis starting material was observed. These results indicate that the Sr sorption mechanism of HAp is influenced by not only its composition but also its crystal morphology.

Energy efficient cement free binder developed from industry waste – A sustainable approach

In this paper, the physicochemical properties and hydration mechanism of cement-free binders developed from fluorogypsum has been discussed. The results showed maximum attainment of strength (38 MPa), low water absorption (<5%) and porosity (<10) with anhydrous calcium chloride and sodium sulphate activators. The enhancement in strength with hydration period was due to the conversion of fluorogypsum into gypsum through formation of intermediate unstable salt. The reaction products were characterised using X-ray diffraction and scanning electron microscopy (SEM) techniques. SEM studies showed the appearance of prismatic and needle-shaped crystals of variable sizes interspersed with anhydrate fluorogypsum plaster which make matrix dense and compact. This change in morphology of anhydrite plaster is responsible for enhancement in strength, reduction in water absorption and porosity of cement-free binders. The engineering properties of the construction materials for use in plastering, masonry works, concrete, blocks and tiles developed from this binder are reported.

A microfluidic-based protein crystallization method in 10 micrometer-sized crystallization space

Protein crystallization and subsequent X-ray diffraction analysis of the three-dimensional structure are necessary for elucidation of the biological functions of proteins and effective rational drug design. Therefore, controlling protein crystallization is important to obtain high resolution X-ray diffraction data. Here, a simple microfluidic method using chips with 10 and 50 μm high crystallization chambers to selectively form suitable single protein crystals for X-ray analysis is demonstrated. As proof of concept, three different types of proteins: lysozyme, glucokinase from Pseudoalteromonas sp. AS-131 (PsGK), and NADPH-cytochrome P450 oxidoreductase–heme oxygenase complex were crystallized. We demonstrate that the crystal growth orientation depends on the height of the crystallization chamber regardless of the protein type. Our results suggest that the confined micro space induces the protein molecules to adhere to a specific crystal face and affects the growth kinetics of each crystal face. The present microfluidic-based protein crystallization method can reform a suitable single protein crystal for X-ray analysis from aggregates of needle-shaped protein crystals.

Significant Improvement of Optoelectronic and Photovoltaic Properties by Incorporating Thiophene in a Solution-Processable D-A-D Modular Chromophore.

Through the incorporation of a thiophene functionality, a novel solution-processable small organic chromophore was designed, synthesized and characterized for application in bulk-heterojunction solar cells. The new chromophore, (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)acrylonitrile) (coded as AS2), was based on a donor–acceptor–donor (D–A–D) module where a simple triphenylamine unit served as an electron donor, 1,4-phenylenediacetonitrile as an electron acceptor, and a thiophene ring as the π-bridge embedded between the donor and acceptor functionalities. AS2 was isolated as brick-red, needle-shaped crystals, and was fully characterized by 1H- and 13C-NMR, IR, mass spectrometry and single crystal X-ray diffraction. The optoelectronic and photovoltaic properties of AS2 were compared with those of a structural analogue, (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(4-(diphenylamino)phenyl)-acrylonitrile) (AS1). Benefiting from the covalent thiophene bridges, compared to AS1 thin solid film, the AS2 film showed: (1) an enhancement of light-harvesting ability by 20%; (2) an increase in wavelength of the longest wavelength absorption maximum (497 nm vs. 470 nm) and (3) a narrower optical band-gap (1.93 eV vs. 2.17 eV). Studies on the photovoltaic properties revealed that the best AS2-[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM)-based device showed an impressive enhanced power conversion efficiency of 4.10%, an approx. 3-fold increase with respect to the efficiency of the best AS1-based device (1.23%). These results clearly indicated that embodiment of thiophene functionality extended the molecular conjugation, thus enhancing the light-harvesting ability and short-circuit current density, while further improving the bulk-heterojunction device performance. To our knowledge, AS2 is the first example in the literature where a thiophene unit has been used in conjunction with a 1,4-phenylenediacetonitrile accepting functionality to extend the π-conjugation in a given D–A–D motif for bulk-heterojunction solar cell applications.

Interface Reactions Between Sealing Glass and Metal Interconnect Under Static and Dynamic Heat Treatment Conditions

Chemical compatibility of sealing glass with metal interconnects is a critical issue for planar solid oxide fuel cell (SOFC). In this paper, interface reactions between a sealing glass and a ferritic metal interconnect (SS410) are tested under three different heat treatment conditions: sealing (static), aging (static), and thermal cycling (dynamic). The results show that the BaCrO4 crystals with two different morphology (round-shaped and needle-shaped) form both at the three-phase boundary (where air, glass, and SS410 meet) and on the surface of the sealing glass under the three conditions. Round-shaped BaCrO4 crystals form with low O2 concentration and short reaction time. Needle-shaped BaCrO4 crystals form with high O2 concentration and long reaction time. For the thermal cycling condition, the BaCrO4 formed at early stages causes the delamination of the sealing interface. Then, O2 diffuses into the interior interface along the delamination path, which results in the formation of BaCrO4 at the interior interface. The delamination-enhanced BaCrO4 formation during thermal cycling will lead to crack along the sealing interface, causing the striking increase of leak rates.