Nanoporous TiO2 Coatings for Infrared Detectors

In GaAs based infrared detectors, a considerable part of the incident light will be reflected at the surface, thus it decreases the detectors sensitivity considerably. In this paper, a TiO₂ nanoporous coating was prepared successfully on the GaAs substrate by sol-gel method. The optical parameters of the coating were also controlled successfully. It was proved that the coating could greatly improve the transmittance of the incident light, which agrees with the theoretical results quite well. In the 2.5–6.0 m waveband, the maximum transmittance of GaAs substrate is 56%, while the transmittance of the GaAs substrate coated with a nanostructured TiO₂ coating is about 94%.     

Synthesis and Characterization of Li‐containing Boron Carbide r‐Li~1B13C2

Transparent and nearly colorless single crystals of r‐LiB₁₃C₂ were obtained by reaction of boron with Li₂CO₃ in a Cu melt at 1250–1300 °C. The structure analysis [R3 m, a = 5.6535(1), c = 12.5320(2) Å, 421 independent reflections, 22 parameters, R₁ = 0.034, wR₂ = 0.093] revealed a crystal structure that can be described as a filling variant of rhombohedral B₁₃C₂. Li⁺ is located in a void above or below the linear CBC unit. The site occupation is close to 50 % resulting in an electron‐precise composition according to Wade's rules if a positive charge is given to the CBC entity: Li⁺(B₁₂)^2–(CBC)⁺. The displacement parameters of the CBC unit indicate disorder in the [001] direction, that relates to the short Li–C distance and the partial occupation of the Li⁺ site. The composition is confirmed by EELS measurements of single crystals. Band gap calculations give a value of 2.94 eV, which is in agreement to the crystals being colorless. The evaluation of the electron density by application of the QTAIM formalism as proposed by Bader modifies the assignment pictured above according to Wade's rules. In agreement to the electronegativities the carbon atoms carry a negative charge (–2.31/–2.42) and the effective charges are: Li^+0.81(B₁₂)^+2.02(CBC)^–2.83.     

纳米木质素/二氧化硅基微胶囊的制备及在自愈合涂层中的应用

利用磷酸化改性木质素/二氧化硅复合纳米颗粒(PAL/SiO₂)作为壁材包埋活性组分异佛尔酮二异氰酸酯(IPDI)制备微胶囊(PAL/SiO₂-IPDI). 通过加入少量反应活性更高的聚合多甲基多二异氰酸酯(PMDI), 与水反应形成聚脲, 以增加微胶囊的壁厚. 采用光学显微镜、 扫描电子显微镜(SEM)和激光粒度分析仪(DLS)研究了PAL/SiO₂复合纳米粒子掺杂量, 水油比和剪切速率对微胶囊表面形貌、 粒径和壁厚的影响. 结果表明, 所制备的微胶囊呈现规整球形, 壁厚为2.36~3.50 μm, 平均粒径为40.3~201.5 μm. IPDI作为芯材包埋在微胶囊中, 芯材含量约为82.8%. 将制备的PAL/SiO₂-IPDI微胶囊添加到环氧树脂中得到自愈合环氧树脂涂层. 其在高盐浓度溶液中的抗侵蚀测试结果显示, 添加质量分数4%的PAL/SiO₂-IPDI微胶囊的环氧树脂涂层在划破后能够快速愈合, 显著降低基底的腐蚀电流和腐蚀速率. 纳米压痕实验表明, 环氧涂层的硬度为249.99 MPa, 而添加PAL/SiO₂-IPDI微胶囊后硬度增加到302.98 MPa, 弹性模量也有提高.     

A Reaction-Induced Localization of Spin Density Enables Thermal C−H Bond Activation of Methane by Pristine FeC4+

The reactivity of the cationic metal-carbon cluster FeC₄⁺ towards methane has been studied experimentally using Fourier-transform ion cyclotron resonance mass spectrometry and computationally by high-level quantum chemical calculations. At room temperature, FeC₄H⁺ is formed as the main ionic product, and the experimental findings are substantiated by labeling experiments. According to extensive quantum chemical calculations, the C−H bond activation step proceeds through a radical-based hydrogen-atom transfer (HAT) mechanism. This finding is quite unexpected because the initial spin density at the terminal carbon atom of FeC₄⁺, which serves as the hydrogen acceptor site, is low. However, in the course of forming an encounter complex, an electron from the doubly occupied sp-orbital of the terminal carbon atom of FeC₄⁺ migrates to the singly occupied π*-orbital; the latter is delocalized over the entire carbon chain. Thus, a highly localized spin density is generated in situ at the terminal carbon atom. Consequently, homolytic C−H bond activation occurs without the obligation to pay a considerable energy penalty that is usually required for HAT involving closed-shell acceptor sites. The mechanistic insights provided by this combined experimental/computational study extend the understanding of methane activation by transition-metal carbides and add a new facet to the dizzying mechanistic landscape of hydrogen-atom transfer.     

PMOXA/PAA Brushes toward on-Line Preconcentration for BSA in Capillary Electrophoresis

In this work, a binary-mixed-brushes-coated (BBC) capillary with switchable protein adsorption/desorption properties was developed and applied for on-line preconcentration of proteins. Firstly, amine-terminated poly(2-methyl-2-oxazoline) (PMOXA-NH₂) and thiolterminated poly(acrylic acid) (PAA-SH) were synthesized by using cationic ring-opening polymerization (CROP) and reversible addition fragmentation chain transfer (RAFT) polymerization, respectively. Then, the BBC capillary based on poly(2-methyl-2-oxazoline) (PMOXA) and poly(acrylic acid) (PAA) was prepared by sequentially grafting of PMOXA-NH₂ and PAA-SH onto fused-silica capillary inner surface through poly(dopamine) (PDA) as an anchor. The obtained PMOXA/PAA coating formed on the capillary or capillary's raw material was characterized in terms of the thickness, surface chemical composition by using scanning electron microscope (SEM) and X-ray photoelectron spectrum (XPS). The switchable protein adsorption/desorption performance of the BBC capillary was investigated by using fluorescence microscope under di erent solutions with certain pH and ionic strength(I). The results showed that bovine serum albumin (BSA) could be adsorbed on BBC capillary at pH=5.0 (I=10^-5 mol/L), and then the adsorbed BSA could be released at pH=9.0 (I=0.1 mol/L). This switchable protein adsorption/desorption property of coated capillary was then used to preconcentrate proteins on-line for increasing the detection sensitivity of BSA in capillary electrophoresis (CE). With this method, a sensitivity enhancement factor (SEF) more than 5000 for BSA detection was obtained.     

In situ fabrication of nanostructured titania coating on the surface of titanium wire: A new approach for preparation of solid-phase microextraction fiber

Nanostructured titania-based solid-phase microextraction (SPME) fibers were fabricated through the in situ oxidation of titanium wires with H₂O₂ (30%, w/w) at 80 °C for 24 h. The obtained SPME fibers possess a ∼1.2 μm thick nanostructured coating consisting of ∼100 nm titania walls and 100-200 nm pores. The use of these fibers for headspace SPME coupled with gas chromatography with electron capture detection (GC-ECD) resulted in improved analysis of dichlorodiphenyltrichloroethane (DDT) and its degradation products. The presented method to detect DDT and its degradation products has high sensitivity (0.20-0.98 ng L⁻¹), high precision (relative standard deviation R.S.D. = 9.4-16%, n = 5), a wide linear range (5-5000 ng L⁻¹), and good linearity (coefficient of estimation R² = 0.991-0.998). As the nanostructured titania was in situ formed on the surface of a titanium wire, the coating was uniformly and strongly adhered on the titanium wire. Because of the inherent chemical stability of the titania coating and the mechanical durability of the titanium wire substrate, this new SPME fiber exhibited long life span (over 150 times).     

Structures and antifouling properties of low surface energy non-toxic antifouling coatings modified by nano-SiO_2 powder

Antifouling coatings are used to improve the speed and energy efficiency of ships by preventing or- ganisms, such as barnacles and weed, building up on the underwater hull and helping the ships movement through the water. Typically, marine coatings are tributyltin self-polishing copolymer paints containing toxic molecules called biocides. They have been the most successful in combating bio- fouling on ships, but their widespread use has caused severe pollution in the marine ecosystem. The low surface energy marine coating is an entirely non-toxic alternative, which reduces the adhesion strength of marine organisms, facilitating their hydrodynamic removal at high speeds. In this paper, the novel low surface energy non-toxic marine antifouling coatings were prepared with modified acrylic resin, nano-SiO2, and other pigments. The effects of nano-SiO2 on the surface structure and elastic modulus of coating films have been studied, and the seawater test has been carried out in the Dalian Bay. The results showed that micro-nano layered structures on the coating films and the lowest surface energy and elastic modulus could be obtained when an appropriate mass ratio of resin, nano-SiO2, and other pigments in coatings approached. The seawater exposure test has shown that the lower the sur- face energy and elastic modulus of coatings are, the less the marine biofouling adheres on the coating films.     

The effect of the sintering atmosphere on the densification of B4C ceramics

Densification of boron carbide during sintering may be improved by a two-stage process, namely heating to 2000°C under vacuum and sintering at 2190°C under argon. This sintering regime allows achieving a relative density of the ceramic bodies fabricated from a fine powder higher than 95%. The nitrogen treatment of the boron carbide phase at 1900°C leads to the formation of the BN phase and precipitation of graphite. Vacuum treatment of these samples at 2000°C leads to decomposition of the boron nitride phase. The liberated free boron may again react with graphite to form in situ boron carbide particles. The experimental investigations of the sintering behavior of the boron carbide phase under various atmospheres supported the thermodynamic predictions regarding the phase transformation. No evidence, however, was found for enhanced sintering under a nitrogen atmosphere.     

Transparent Conducting Films in the Zn--Sn--O Tie Line

Two Er³⁺/Yb³⁺ monolithic silica-alumina xerogels doped with different Yb³⁺ concentrations were prepared by sol–gel route. The samples were thermally treated in air at 950°C for 120 h, and Raman and UV-visible-NIR spectroscopy were used to monitor the degree of densification of the glasses and the residual OH     

Preparation, Characterization and Catalytic Properties of S2O8^2-／ZrO2 Supported by Tungsten Carbide

A WC-supported S2O8^2-/ZrO2(PSZ) catalyst was prepared and characterized by means of XRD, BET, FTIR and XPS. The isomerization of n-pentane over the catalyst was investigated as well. The results show that the skeletal isomerization and the crack of n-pentane proceed simultaneously on WC-supported S2O8^2-/ZrO2 catalyst. The addition of tungsten carbide showed a significant enhancement in the activity and stability of the catalyst for n-pentane isomerization. The catalyst showed evidently a better activity than S2O8^2-/ZrO2 supported by Pt and WO3. The results can be interpreted by the existence of the tungsten oxycarbide compound(WCxOy) with carbidic, oxide and acidic sites.