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1.
We describe a new coating method Laminar Flow Coating (LFC) technique developed to obtain highly reflective (HR) laser damage resistant sol-gel multidielectric coatings. Such coatings are used in high-power lasers for inertial confinement fusion experiments (ICF). This technique uses substrates in an upside-down position and a travelling wave of coating solution is transported with a laminar motion under the substrate surface with a tubular dispense unit. This creates a thin-film coating by solvent evaporation. Satisfactory results have been obtained on 20-cm square glass substrates regarding the optical performances, the thickness uniformity, the edge-effects and the laser damage resistance. This deposition technique combines the advantages of both classical techniques: the non-exclusive substrate geometry such as in dip-coating and the small solution consumption such as in spin-coating.The association of sol-gel colloidal suspensions and LFC coating process has been demonstrated as a promising way to produce inexpensive specific optical coatings [1].  相似文献   

2.
PceA is a cobalamin‐dependent reductive dehalogenase that catalyzes the dechlorination of perchloroethylene to trichloroethylene and then to cis‐dichloroethylene as the sole final product. The reaction mechanism and the regioselectivity of this enzyme are investigated by using density functional calculations. Four different substrates, namely, perchloroethylene, trichloroethylene, cis‐dichloroethylene, and chlorotheylene, have been considered and were found to follow the same reaction mechanism pattern. The reaction starts with the reduction of CoII to CoI through a proton‐coupled electron transfer process, with the proton delivered to a Tyr246 anion. This is followed by concerted C?Cl bond heterolytic cleavage and proton transfer from Tyr246 to the substrate carbon atom, generating a CoIII?Cl intermediate. Subsequently, a one‐electron transfer leads to the formation of the CoII?Cl product, from which the chloride and the dehalogenated product can be released from the active site. The substrate reactivity follows the trend perchloroethylene>trichloroethylene?cis‐dichloroethylene?chlorotheylene. The barriers for the latter two substrates are significantly higher compared with those for perchloroethylene and trichloroethylene, implying that PceA does not catalyze their degradation. In addition, the formation of cis‐dichloroethylene has a lower barrier by 3.8 kcal mol?1 than the formation of trans‐dichloroethylene and 1,1‐dichloroethylene, reproducing the regioselectivity. These results agree quite well with the experimental findings, which show cis‐dichloroethylene as the sole product in the PceA‐catalyzed dechlorination of perchloethylene and trichloroethylene.  相似文献   

3.
Multilayered diamond‐like carbon (DLC) nanocomposite coating has been deposited on silicon and stainless steel substrates by combination of cathodic arc evaporation and magnetron sputtering. In order to make DLC coating adhered to metal substrate, a chromium interlayer has been deposited with constant bias voltage of −150 V applied to the substrate. Dense multilayered coating consists of metallic or nonmetallic and tetrahedral carbon (ta‐C) layers with total thickness of 1.44 μm. The coating has been studied for composition, morphology, surface nature, nanohardness, corrosion resistance, and tribological properties. The composition of the coating has been estimated by energy‐dispersive spectroscopy. Field‐emission scanning electron microscopy and atomic force microscopy have been used to study the surface morphology and topography. ID/IG ratio of ta‐C:N layer obtained from Raman spectroscopy is 1.2, indicating the disorder in the layer. X‐ray photoelectron spectroscopy studies of individual ta‐C:N, CrN, and Cr‐doped DLC layers confirm the presence of sp2C, sp3C, CrN, Cr2N, and carbidic carbon, and sp2C, sp3C, and Cr carbide. Nanohardness studies show the maximum penetration depth of 70 to 85 nm. Average nanohardness of the multilayered DLC coating is found to be 35 ± 2.8 GPa, and Young's modulus is 270 GPa. The coating demonstrates superior corrosion resistance with better passivation behavior in 3.5% NaCl solution, and corrosion potential is observed to move towards nobler (more positive) values. A low coefficient of friction (0.11) at different loads is observed from reciprocating wear studies. Wear volume is lower at all loads on the multilayered DLC nanocomposite coating compared to the substrate.  相似文献   

4.
h‐BN, as an isoelectronic analogue of graphene, has improved thermal mechanical properties. Moreover, the liquid‐phase production of h‐BN is greener since harmful oxidants/reductants are unnecessary. Here we report a novel hybrid architecture by employing h‐BN nanosheets as 2D substrates to load 0D Fe3O4 nanoparticles, followed by phenol/formol carbonization to form a carbon coating. The resulting carbon‐encapsulated h‐BN@Fe3O4 hybrid architecture exhibits synergistic interactions: 1) The h‐BN nanosheets act as flexible 2D substrates to accommodate the volume change of the Fe3O4 nanoparticles; 2) The Fe3O4 nanoparticles serve as active materials to contribute to a high specific capacity; and 3) The carbon coating not only protects the hybrid architecture from deformation but also keeps the whole electrode highly conductive. The synergistic interactions translate into significantly enhanced electrochemical performances, laying a basis for the development of superior hybrid anode materials.  相似文献   

5.
Abstract

Benzylated glycals, unlike their acylated congeners which easily undergo allylic rearrangement, are frequently employed as reactive enol ether type substrates in a variety of electrophilic addition reactions.1–4 Although these compounds are considered to be readily available substrates, reported procedures for their syntheses involve some steps of limited efficiency, chromatographic separations or costly reagents,5–7 and experimental requirements not amenable for large scale preparations. In view of the recent applications of benzylated glycals to syntheses of O-glycosides,1,2 C-glycosyl compounds,3 and β-lactams,4 we have undertaken a study aimed at efficient one step benzylation procedures applicable to pyranoid 1-enitols as well as to their acylated derivatives. This goal was eventually achieved by employing a catalytic phase transfer alkylation system with  相似文献   

6.
The chemoselectivity between S-oxidation and hydrogen atom transfer (HAT) from C−H bonds has been investigated in the oxidations of a series of aryl sulfides, alkyl aromatic compounds and benzylic alcohols promoted by the iron(IV)-oxo complex [(N4Py)FeIV(O)]2+ (N4Py: N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)-methylamine) either alone or in the presence of the N-hydroxyphthalimide (NHPI) mediator via kinetic and product studies. Kinetic analyses indicate a generally higher reactivity of [(N4Py)FeIV(O)]2+ for S-oxidation process while HAT is favored in the reactions promoted by phthalimide-N-oxyl radical (PINO) deriving from NHPI oxidation. Product analysis in intermolecular competitive oxidations confirms the kinetic results with sulfoxides obtained as major products in the oxidation promoted by [(N4Py)FeIV(O)]2+. Conversely, when NHPI is employed as a mediator, significant differences in terms of chemoselectivity are observed, and HAT-derived products are obtained in higher yields which translate into an inversion of selectivity in the case of the substrates containing activated C−H bonds like diphenylmethane, triphenylmethane and benzylic alcohols. A similar change of chemoselectivity is also observed in the oxidation of aromatic substrates containing both a sulfur atom and α to OH benzylic C−H bonds, with the sulfoxide product more abundant in the absence of NHPI and carbonyl products prevailing with the [(N4Py)FeIV(O)]2+/NHPI system.  相似文献   

7.
Nanostructured coatings have recently attracted increasing interest because of the possibilities of synthesizing materials with unique physical-chemical properties. Highly sophisticated surface related properties, such as optical, magnetic, electronic, catalytic, mechanical, chemical and tribological properties can be obtained by advanced nanostructured coatings, making them attractive for various industrial applications. In this report we describe our efforts at developing methodology for the fabrication of SrFeO3-x based thin films using a modified Pechini method. Thin films of SrFeO3-x were fabricated using spin coating and a drop coating method developed in-house on Al2O3 and Si- substrates. The films annealed at 600°C for one hour show a perovskite phase. The grain size increases with increase in annealing temperature. The influence of various variables such as metal to chelant ratio, drying control reagents, calcination conditions, substrate type and mode of film formation were studied using XRD, optical microscopy, SEM and AFM.  相似文献   

8.
Transparent, conductive composite coatings were fabricated from suspensions of poly(vinyl acetate‐acrylic) (PVAc‐co‐acrylic) copolymer latices (50–600 nm) and nanosized antimony‐doped tin oxide (ATO) particles (~15 nm). The suspensions were deposited as coatings onto poly(ethylene terephthalate) substrates and dried at 50 °C. Microstructure studies using field emission scanning electron microscopy and tapping‐mode atomic force microscopy (TMAFM) indicated that the latex particles coalesced during drying and forced the ATO particles to segregate into the boundaries between the latex particles. Low phase contrast was observed with TMAFM; this result was consistent with the presence of PVAc‐co‐acrylic in the ATO‐rich phase of the composite. The conductivity of the composite coatings followed a percolation power‐law equation, with the percolation threshold between 0.05 and 0.075 volume fractions of ATO and the critical conductivity exponent ranging from 1.34 to 2.32. The highest direct‐current conductivity of the composite coatings was around 10?2 S/cm. The optical transmittance and scattering behavior of the coatings were also investigated. Compared with the PVAc‐co‐acrylic coating, the composite coatings had lower transparency because of the Rayleigh scattering. The transparency of the composite coatings was improved by a reduction in the coating thickness. The best transparency for the coatings with a direct‐current conductivity of approximately 10?2 S/cm was around 85% at a wavelength of 600 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1744–1761, 2003  相似文献   

9.
The substituted isoborneols 1a – 1g and 5,6‐dehydroisoborneols 6a – 6c , readily prepared in excellent yields from (+)‐camphor and (+)‐5,6‐dehydrocamphor ( 2 ) by aryl, vinyl, or alkyl Grignard addition in the presence of stoichiometric amounts of CeCl3, were thermally isomerized in a flow reactor system under DGPTI (dynamic gas‐phase thermo‐isomerization) conditions at temperatures between 480 and 630° to give the enantiomerically pure monocyclic carbonyl compounds 7a – 7d, 19a , b, 23 , and 24 . In all cases, product formation proceeded highly regio‐ as well as stereoselectively. The absolute configurations of the new stereogenic centers were determined by 1H‐NOE measurements. DGPTI of the aryl substrates 1a – 1d is proposed to effect initial cleavage of the weakest single bond in the molecule under formation of a diradical intermediate state followed by intramolecular H‐abstraction to afford the acetophenone derivatives 7a – 7d . This reaction path was further supported by a 2H‐labeling study showing the OH group to be the exclusive H‐source. In contrast, DGPTI of the vinyl substrates 1e and 6b allowed concerted retro‐ene and oxy‐Cope rearrangements. In the case of 5,6‐dehydro‐2‐phenylisoborneol ( 6a ), concomitant diradical and retro‐DielsAlder reaction pathways could be observed. In addition, a new route to (+)‐transα‐campholanic acid ( 9 ) and (+)‐transα‐dihydrocampholytic acid ( 14 ) is presented by regioselective BaeyerVilliger oxidation and subsequent hydrolysis of 7c and 7d , respectively.  相似文献   

10.
An ultra-thin layer of polypyrrole can be coated on non-conducting substrates, e.g., acrylic, by dip coating into a colloidal suspension of polypyrrole. This thin coating reversibly combines with low concentrations of ammonia or hydrazine with a concomitant reversible increase in resistance; 0.1 μg cm?3 of ammonia can readily be detected with a 1 cm2 area of sensor.  相似文献   

11.
Tri-iso-amyl phosphate (TAP), an indigenously prepared extractant was utilized for reactor fuel reprocessing and compared with tri-butyl phosphate (TBP) and tri-n-hexyl phosphate (THP). The potential of these extractants was found to be in the order TAP>THP>TBP by calculating the acid uptake value (K H). The effect of various parameters such as solvent degradation due to acid hydrolysis, radiation effect, decontamination factor and phase separation were investigated and it was found that TAP was always a better extractant in comparison to THP and TBP. In addition to this, the extraction of fission product contaminants such as 144Ce, 137Cs, 106Ru, 95Zr was almost negligible, even at very high nitric acid concentrations in the aqueous phase, indicating the potential application of TAP in actinide partitioning. Sodium carbonate solution or acidified distilled water was a good strippant for U(VI), similarly, uranium(IV) nitrate stripped Pu(IV) from the organic phase.  相似文献   

12.
Electrochromic devices (ECDs) were prepared on flexible substrates using spray coating and slot‐die coating methods. The electrochromic materials were the conjugated electroactive polymers, poly((2,2‐bis(2‐ethylhexyloxymethyl)‐propylene‐1,3‐dioxy)‐3,4‐thiophene‐2,5‐diyl) as a vibrantly colored active material (ECP‐Magenta) and poly(N‐octadecyl‐(propylene‐1,3‐dioxy)‐3,4‐pyrrole‐2,5‐diyl) as a minimally colored, charge balancing material (MCCP). Two electrolyte systems were compared to allow development of fully printable and laminated devices on flexible substrates. Devices of various sizes, up to 7 × 8 cm2, are demonstrated with pixelated devices containing pixel sizes of 4 × 4 mm2 or 13 × 13 mm2. The transmission contrast exhibited by the devices, when switched between the fully bleached and fully colored state, was 58% at a visible wavelength of 550 nm, and the devices exhibited switching times of <10 s. Additionally, we demonstrate the utilization of printed organic photovoltaic devices (with or without the use of a lithium‐polymer battery) to power the devices between the colored and bleached state, illustrating a self‐powered ECD. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

13.
Summary Functional coating and surface modified layers can be characterized by engineering related criteria such as the ultramicrohardness test and the scratch adhesion test. The ultramicrohardness test is based on penetration depth measurements during a loading and unloading cycle. The depth sensing indentation provides a means of evaluating the elastic and plastic deformations of the tested material, from which, by calculation, the microhardness, HV, and the elasticity modulus, E, can be derived as illustrated on a number of examples of hard and soft materials and coating composites. The scratch test (REVETESTR) and microscratch test (MSTR) has been applied to determine the adhesive and/or cohesive strength of coatings deposited on softer or tougher substrates. A Rockwell C diamond cone is used to scratch the surface of the coated or surface-modified specimen at a constant speed and under a continuously increasing load. The smallest load at which the coating is damaged, called the Critical Load, Lc, is determined by optical, electron optical, acoustic emission detection and/or by frictional force measurement, i.e. by the sudden increase of the driving force. This is illustrated on hard, brittle, and on soft coatings.  相似文献   

14.
A continuous‐flow process based on a chiral transition‐metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO2) as the mobile phase is presented for asymmetric catalytic transformations of low‐volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high‐pressure continuous‐flow setup, the product was isolated in analytically pure form without the use of any organic co‐solvent and with no detectable catalyst leaching. Phase‐behaviour studies and high‐pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO2. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long‐term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L ?1 h?1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger‐scale application.  相似文献   

15.
This work unveils the reactivity patterns, as well as ligand and additive effect on alkali-metal-base-catalyzed transfer hydrogenation of ketones. Crucially to this reactivity is the presence of a Lewis acid (alkali cation), as opposed to a simple base effect. With aryl ketones, the observed reactivity order is Na+>Li+>K+, whereas for aliphatic substrates it follows the expected Lewis acidity, Li+>Na+>K+. Importantly, the reactivity pattern can be drastically changed by adding ligands and additives. Kinetic, labelling, and competition experiments as well as DFT calculations suggested that the reaction proceeds through a concerted direct hydride-transfer mechanism, originally suggested by Woodward. The lithium cation was found to be intrinsically more active than heavier congeners, but in the case of aryl ketones a decrease in reaction rate was observed at ≈40 % conversion with lithium cations. Noncovalent-interaction analysis revealed that this deceleration effect originated from specific noncovalent interactions between the aryl moiety of 1-phenylethanol and the carbonyl group of acetophenone, which stabilize the product in the coordination sphere of lithium and thus poison the catalyst. The ligand/additive effect is a complicated phenomenon that includes a combination of several factors, such as the decrease of activation energy by ligation (confirmed by distortion/interaction calculations of N,N,N’,N’-tetramethylethylenediamine, TMEDA) and the change in relative stabilization of reagents and substrates in the solution and the coordination sphere of the metal. Finally, we observed that lithium-base-catalyzed transfer hydrogenation can be further facilitated by the addition of an inexpensive and benign reagent, LiCl, which likely operates by re-initiating the reaction on a new lithium center.  相似文献   

16.
Poly(p‐phenylene vinylene) (PPV), poly(2,5‐dioctyl‐p‐phenylene vinylene) (PDOPPV), and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylene vinylene] (MEHPPV) were synthesized by a liquid–solid two‐phase reaction. The liquid phase was tetrahydrofuran containing 1,4‐bis(bromomethyl)benzene, 1,4‐bis(chloromethyl)‐2,5‐dioctylbenzene, or 1,4‐bis(chloromethyl)‐2‐methoxyl‐5‐(2′‐ethylhexyloxy)benzene as the monomer and a certain amount of tetrabutylammonium bromide as a phase‐transfer catalyst. The solid phase consisted of potassium hydroxide particles with diameters smaller than 2 mm. The experimental results demonstrated that the reaction conversions of PPV and PDOPPV were fairly high (~65%), but the conversion of MEHPPV was only 45%. Moreover, gelation was found in the polymerization processes. As a result, PPV was insoluble and PDOPPV and MEHPPV were partially soluble in the usual organic solvents, such as tetrahydrofuran and chloroform. Soluble PDOPPV and MEHPPV were obtained with chloromethylbenzene or bromomethylbenzene as a retardant regent. The molar mass of soluble PDOPPV was measured to be 2 × 104 g mol?1, and that of MEHPPV was 6 × 104 g mol?1. A thin, compact film of MEHPPV was formed via spin coating, and it emitted a yellow light. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 449–455, 2003  相似文献   

17.
Herein, we introduce a facile, user‐ and environmentally friendly (n‐octanol‐induced) oleic acid (OA)/ionic liquid (IL) two‐phase system for the phase‐ and size‐controllable synthesis of water‐soluble hexagonal rare earth (RE=La, Gd, and Y) fluoride nanocrystals with uniform morphologies (mainly spheres and elongated particles) and small sizes (<50 nm). The unique role of the IL 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BmimPF6) and n‐octanol in modulating the phase structure and particle size are discussed in detail. More importantly, the mechanism of the (n‐octanol‐induced) OA/IL two‐phase system, the formation of the RE fluoride nanocrystals, and the distinctive size‐ and morphology‐controlling capacity of the system are presented. BmimPF6 is versatile in term of crystal‐phase manipulation, size and shape maintenance, and providing water solubility in a one‐step reaction. The luminescent properties of Er3+‐, Ho3+‐, and Tm3+‐doped LaF3, NaGdF4, and NaYF4 nanocrystals were also studied. It is worth noting that the as‐prepared products can be directly dispersed in water due to the hydrophilic property of Bmim+ (cationic part of the IL) as a capping agent. This advantageous feature has made the IL‐capped products favorable in facile surface modifications, such as the classic Stober method. Finally, the cytotoxicity evaluation of NaYF4:Yb,Er nanocrystals before and after silica coating was conducted for further biological applications.  相似文献   

18.
The stereoselective Rauhut–Currier (RC) reaction catalyzed by a cysteine derivative has been explored computationally with density functional theory (M06‐2X). Both methanethiol and a chiral cysteine derivative were studied as nucleophiles. The complete reaction pathway involves rate‐determining elimination of the thiol catalyst from the Michael addition product. The stereoselective Rauhut–Currier reaction, catalyzed by a cysteine derivative as a nucleophile, has also been studied in detail. This reaction was experimentally found to be extremely sensitive to the reaction conditions, such as the number of water equivalents and the effect of potassium counterion. The E1cB process for catalyst elimination has been explored computationally for the eight possible stereoisomers. The effect of explicit water solvation and the presence of counterion (either K+ or Na+) has been studied for the lowest energy enantiomer pair (1S, 2R, 3S)/(1R, 2S, 3R).  相似文献   

19.
Titania-lanthanum phosphate nanocomposites with multifunctional properties have been synthesized by aqueous sol-gel method. The precursor sols with varying TiO2:LaPO4 ratios were applied as thin coating on glass substrates in order to be transparent, hydrophobic, photocatalytically active coatings. The phase compositions of the composite powders were identified by powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). The anatase phase of TiO2 in TiO2-LaPO4 composite precursors was found to be stable even on annealing at 800 °C. The glass substrates, coated with TL1 (TiO2-LaPO4 composition with 1 mol% LaPO4) and TL50 (composite precursor containing TiO2 and LaPO4 with molar ratio 1:1) sols and annealed at 400 °C, produced contact angles of 74° and 92°, respectively, though it is only 62° for pure TiO2 coating. The glass substrates, coated with TL50 sol, produced surfaces with relatively high roughness and uneven morphology. The TL1 material, annealed at 800 °C, has shown the highest UV photoactivity with an apparent rate constant, kapp=24×10−3 min−1, which is over five times higher than that observed with standard Hombikat UV 100 (kapp=4×10−3 min−1). The photoactivity combined with a moderate contact angle (85.3°) shows that this material has a promise as an efficient self-cleaning precursor.  相似文献   

20.
In the present study, maleimide‐modified epoxide resin containing UV‐curable hybrid coating materials were prepared and coated on polycarbonate substrates in order to improve their surface properties. UV‐curable, bismaleimide‐modified aliphatic epoxy resin was prepared from N‐(p‐carboxyphenyl) maleimide (p‐CPMI) and cycloaliphatic epoxy (Cyracure‐6107) resin. The structure of the bismaleimide modified aliphatic epoxy resin was analyzed by FTIR and the characteristic absorption band for maleimide ring was clearly observed at 3100 cm?1. Silica sol was prepared from tetraethylorthosilicate (TEOS) and methacryloxy propyl trimethoxysilane (MAPTMS) by sol–gel method. The coating formulations with different compositions were prepared from UV‐curable bismaleimide‐based epoxy oligomer and sol–gel mixture. The molecular structure of the hybrid coating material was analyzed by 29Si‐CP/MAS NMR spectroscopy techniques. In the 29Si CP/MAS NMR spectrum of the hybrid coating, mainly two kinds of signals were observed at ?68 and ?110 ppm that correspond to T3 and Q4 peaks, respectively. This result shows that a fully condensed structure was obtained. The thermal and morphological properties of these coatings materials were investigated by using TGA and SEM techniques. Hardness and abrasion resistance properties of coating materials were examined and both were found to increase with sol–gel precursor content of the coating. The photopolymerization kinetics was investigated by using RT‐IR. 70% conversion was attained with the addition of 15 wt% of BMI resin into the acrylate‐based coating formulation. It was found that the UV‐curable organic–inorganic hybrid coatings improved the surface properties of polycarbonate. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

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