宽温快速阳极氧化工艺

宽温快速阳极氧化工艺与常规阳极氧化工艺相比工作温度宽，工作时间缩短了25％左右，在同等工作电流情况下，槽电压也有所降低，适用于铝和铝合金阳极氧化、染色和电解着色生产线，膜层质量完全符合国家标准。     

铝及铝合金宽温硬质阳极氧化工艺应用

铝及铝合金硬质阳极氧化膜 ,除有其功能性的硬度之外 ,还具有很高的抗蚀性 ,尤其在工业大气和海洋气候环境之中。因其转化膜为非晶态结构、孔隙率低、阻挡层厚 ,因而耐腐蚀性强、硬度高、耐磨性好 ,广泛应用于汽车、摩托车及机电产品等零部件。目前 ,在光电产品上也得到应用。我厂采用的宽温硬质阳极氧化工艺 ,一般在常温下进行氧化 ,且比硫酸型和草酸型硬质阳极氧化在溶液维护和操作上更简便。1　工艺及操作条件除油→上挂具→碱蚀 (可不进行 )→水洗→出光→水洗→宽温硬质阳极氧化→水洗→热水封闭→干燥 (烘干或吹干 )→检验。乳酸 (工…     

铝合金在大脉冲电流下的快速成膜工艺及微观组织分析

采用阳极氧化表面处理的方法对铝活塞顶面进行处理,开发了一种在大脉冲电流下在活塞表面上快速生成一层厚阳极氧化膜的工艺方法,讨论了各种主要氧化条件如H2SO4浓度、添加剂、电流密度、电解液温度、电压及时间等对此快速成膜的影响,并用扫描电镜SEM对其微观组织进行了分析.     

铝型材阳极氧化工艺技术现状和展望

综述了国内外铝材阳极氧化的工艺技术现状,着重介绍了建筑铝型材阳极氧化着色工艺的进步,以及电解着色添加剂的研制和应用等。     

稀土在金属表面处理工艺中的应用技术(7)——稀土铝及其合金宽温耐蚀耐磨硫酸阳极氧化工艺技术

介绍了在铝及其合金的硫酸阳极氧化工艺中,添加以稀土为主要材料的添加剂,可使铝硫酸阳极氧化的温度范围变宽;氧化膜的耐蚀性和耐磨性能得到明显的提高.同时,还介绍了铝硫酸阳极氧化生产操作时各工艺因素对铝氧化的影响以及故障造成的原因.     

有机添加剂在镁合金阳极氧化中的研究进展

镁合金阳极氧化及微弧氧化电解液中少量的有机添加剂对氧化膜的质量及性能起着至关重要的作用。综述了近年来在镁合金阳极氧化及微弧氧化中有机添加剂的最新研究现状及研究进展,介绍了有机添加剂在镁合金阳极氧化中的作用机制研究现状,指出绿色环保、成本低廉的有机添加剂是镁合金阳极氧化添加剂选择的主要方向,对有机添加剂在镁合金阳极氧化中的作用机制的进一步深入研究是迫切需要解决的科学问题。     

AZ31镁合金无铬阳极氧化新工艺

为了提高镁合金的耐腐蚀性能,采用直流阳极氧化工艺研究了一种新型无Cr环保型镁合金阳极氧化配方及工艺.溶液主要成分包含NaOH、Na3PO4、KF、铝盐和适量添加剂.结果表明,氧化膜主要由MgO和MgAl2O4组成;该环保型阳极氧化新工艺所获得的膜层的耐腐蚀性能等级为9级,优于传统的HAE工艺(8级),对AZ31镁合金能提供更有效的保护.     

铝合金常温脉冲硬质阳极氧化膜性能的研究

采用正交试验研究了添加剂、电解液温度、电流密度、占空比等对常温脉冲硬质阳极氧化膜硬度、厚度及耐腐蚀性的影响，确定了最佳工艺条件。结果表明，新工艺提高了硬质氧化膜的硬度和生成速度，并将氧化温度提高到了30℃。在最佳工艺条件下，氧化膜硬度为516HV，厚度为0．0342mm。点滴试验表明，脉冲硬质阳极氧化膜耐腐蚀性能优异。     

脉冲阳极氧化工艺制作GaAs／AlGaAs宽条形半导体激光器

研究了脉冲阳极氧化工艺的特性,并利用脉冲阳极氧化工艺制作出激射波长为776nm的宽条形半导体激光器,器件阚值电流为0.35A,斜率效率为1.12W/A,与常规工艺制作的器件相比阈值电流降低了22%,斜率效率提高了18%.     

原位合成TiB2/6351Al复合材料阳极氧化的研究

颗粒增强铝基复合材料强度及模高量,具有很大的应用前景,但增强颗粒的引入使复合材料的耐蚀性大大下降,同时也给其阳极氧化带来困难.为此,将阳极氧化工艺运用于一种原位合成TiB2/6351Al复合材料,研究了阳极氧化液成分、添加剂、氧化电流密度、温度和时间对膜层质量的影响.对膜层的性能测试表明,所得氧化膜大大提高了材料的耐蚀性能.此外,通过对氧化膜表面与截面结构的深入观察,分析了该复合材料氧化膜的生长机理.     

Cobalt 1,3-Diisopropyl-1H-imidazol-2-ylidene Complexes: Synthesis, Solid-State Structures, and Quantum Chemistry Calculations

The reaction of (η(5)-C(5)H(5))Co(PPh(3))(2) with 1,3-bis(isopropyl)imidazol-2-ylidene (Im(i)Pr(2)) leads to the formation of (η(5)-C(5)H(5))Co(PPh(3))(Im(i)Pr(2)). In a similar fashion (η(5)-C(5)H(5))Co(Im(i)Pr(2))(CO) is formed from (η(5)-C(5)H(5))Co(CO)(2). The barrier to rotation about the Co-C(carbene) bond in the latter complex has been determined by variable-temperature (1)H NMR spectroscopy (13.6 kcal/mol) and by computation (13.3 kcal/mol). The structural and dynamic properties of (η(5)-C(5)H(5))Co(ImMe(2))(CO) (ImMe(2) = 1,3-dimethylimidazol-2-ylidene) and (η(5)-C(5)H(5))Co(ImAr(2))(CO) (ImAr(2) = 1,3-dimesityl-2-ylidene) were examined by quantum chemistry calculations.     

Preparation and characterization of SiO2-pillared H2Ti4O9 and its photocatalytic activity for methylene blue degradation

SiO(2) pillared layered titanate (SiO(2)-H(2)Ti(4)O(9)) was prepared via intercalating organosilanes into the interlayers of the layered K(2)Ti(4)O(9) followed by calcination at 500 degrees C. The resulting materials were characterized using XRD, N(2) adsorption-desorption isotherms, UV-vis spectra, IR spectroscopy and Raman spectroscopy. The photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was evaluated by photocatalytic degradation of aqueous methylene blue dye (MB). XRD and specific surface area results showed that SiO(2)-H(2)Ti(4)O(9) had an interlayer distance of 1.45 nm and a specific surface area of 148 m(2)g(-1). UV-vis absorption spectrum of SiO(2)-H(2)Ti(4)O(9) showed a red shift, indicative of a narrower band gap compared to K(2)Ti(4)O(9). In addition, SiO(2)-H(2)Ti(4)O(9) showed higher MB adsorption capacity compared to H(2)Ti(4)O(9) and K(2)Ti(4)O(9). MB photodegradation over H(2)Ti(4)O(9), K(2)Ti(4)O(9) and SiO(2)-K(2)Ti(4)O(9) followed zero-order kinetics under our experimental conditions, and the photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was found to be three times higher than that of K(2)Ti(4)O(9), which could be attributed to the increase of interlayer space and specific surface area of SiO(2)-pillared layered titanate.     

Tributyl phosphate as a sensitivity-enhancing solvent for organotin in carbon furnace atomic absorption spectrometry

Tributyl phosphate (TBP) has been found to be a sensitivity-enhancing solvent for organotin compounds in graphite furnace atomic absorption spectrometry; (C(4)H(9))(2)Sn(O(2)CCH(3))(2), (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2), (C(4)H(9))(3)SnCl, and (C(4)H(9))(4)Sn all give 1 order of magnitude higher sensitivities in TBP than in toluene or ethyl acetate. The sensitivities are enhanced further 1-2 orders of magnitude in TBP, when PdCl(2)(CH(3)CN)(2) is added as a matrix modifier in the organic solvent. Among the four organotin compounds, (C(4)H(9))(2)Sn(O(2)CCH(3))(2) and (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2) give better sensitivities than (C(4)H(9))(3)SnCl and (C(4)H(9))(4)Sn in the absence of palladium in any organic solvent, which suggests that the oxygen atom in the tin compound might form tin oxides that are resistant to volatilization loss during ashing. Scanning electron microscopic, electrothermal vaporization ICPMS, and powder X-ray diffraction studies show that the final products before atomization include phosphorus-containing compounds Sn(2)P(2)O(7), SnP(2)O(7), and Pd(9)P(2), besides tin-palladium alloys, PdSn, Pd(3)Sn, Pd(2)Sn, Pd(3)Sn(2), and PdSn(3). These phosphorus-containing compounds would more efficiently stabilize tin and suppress tin vaporization loss during ashing, to give higher sensitivity.     

Emission properties of hydrothermal Yb(3+), Er(3+) and Yb(3+), Tm(3+)-codoped Lu2O3 nanorods: upconversion, cathodoluminescence and assessment of waveguide behavior

Yb(3+) and Ln(3+) (Ln(3+) = Er(3+) or Tm(3+)) codoped Lu(2)O(3) nanorods with cubic Ia3 symmetry have been prepared by low temperature hydrothermal procedures, and their luminescence properties and waveguide behavior analyzed by means of scanning near-field optical microscopy (SNOM). Room temperature upconversion (UC) under excitation at 980 nm and cathodoluminescence (CL) spectra were studied as a function of the Yb(+) concentration in the prepared nanorods. UC spectra revealed the strong development of Er(3+) (4)F(9/2) → (4)I(15/2) (red) and Tm(3+) (1)G(4) → (3)H(6) (blue) bands, which became the pre-eminent and even unique emissions for corresponding nanorods with the higher Yb(3+) concentration. Favored by the presence of large phonons in current nanorods, UC mechanisms that privilege the population of (4)F(9/2) and (1)G(4) emitting levels through phonon-assisted energy transfer and non-radiative relaxations account for these observed UC luminescence features. CL spectra show much more moderate development of the intensity ratio between the Er(3+) (4)F(9/2) → (4)I(15/2) (red) and (2)H(11/2), (4)S(3/2) → (4)I(15/2) (green) emissions with the increase in the Yb(3+) content, while for Yb(3+), Tm(3+)-codoped Lu(2)O(3) nanorods the dominant CL emission is Tm(3+) (1)D(2) → (3)F(4) (deep-blue). Uniform light emission along Yb(3+), Er(3+)-codoped Lu(2)O(3) rods has been observed by using SNOM photoluminescence images; however, the rods seem to be too thin for propagation of light.     

Pulsed laser photofragment emission for detection of mercuric chloride

The viability of pulsed laser photofragment emission (PFE) is evaluated for the in situ measurement of vapor-phase mercuric chloride (HgCl(2)) concentration in combustion flue gas. Dispersed emissions from both the Hg (6(3)P(1)) and HgCl (B(2)Sigma(+)) photoproducts are presented, and the dependence of the HgCl(2) PFE signal originating from Hg (6(3)P(1)) on the collisional environment is examined for buffer-gas mixtures of N(2), O(2), and CO(2). Integrated PFE intensity measurements as a function of buffer gas pressure support the assumption that the primary effect of the relevant flue gas constituents is to quench emission from Hg (6(3)P(1)). The quenching rate constants for PFE from HgCl(2) were measured to be 1.37 (+/-0.16) x 10(5) Torr(-1) s(-1) for N(2), 9.35 (+/-0.25) x 10(6) Torr(-1) s(-1) for O(2), and 1.49 (+/-0.29) x 10(6) Torr(-1) s(-1) for CO(2). These values are in good accord with literature values for the quenching of Hg (6(3)P(1)). The emission cross section for Hg (6(3)P(1)) generated by photodissociation of HgCl(2) in 760 Torr N(2) is found to be 1.0 (+/-0.2) x 10(-25) m(2) by comparing the PFE signal to N(2) Raman scattering.     

Scope and Mechanistic Study of the Coupling Reaction of α, β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C-H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1](1)[propene](0)[cinnamate](-1). A negligible deuterium kinetic isotope effect (k(H)/k(D) = 1.1±0.1) was measured from both (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) and (E)-C(6)H(5)CD=C(CH(3))CONHCH(3) with styrene. In contrast, a significant normal isotope effect (k(H)/k(D) = 1.7±0.1) was observed from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene and styrene-d(10). A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C(6)H(5)CH=CHCO(2)Et with propene ((13)C(recovered)/(13)C(virgin) at C(β) = 1.019(6)), while a negligible carbon isotope effect ((13)C(recovered)/(13)C(virgin) at C(β) = 0.999(4)) was obtained from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene. Hammett plots from the correlation of para-substituted p-X-C(6)H(4)CH=CHCO(2)Et (X = OCH(3), CH(3), H, F, Cl, CO(2)Me, CF(3)) with propene and from the treatment of (E)-C(6)H(5)CH=CHCO(2)Et with a series of para-substituted styrenes p-Y-C(6)H(4)CH=CH(2) (Y = OCH(3), CH(3), H, F, Cl, CF(3)) gave the positive slopes for both cases (ρ = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, Δ H(?) = 20±2 kcal mol(-1) and S(?) = -42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies.     

Non-Redox Assisted Oxygen-Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp(2)Ti(eta-OOBu)L], L = Cl, OTf, Br, OEt(2), Et(3)P

The titanium(IV) alkylperoxide complex Cp(2)Ti(OO(t)Bu)Cl (1) is formed on treatment of Cp(2)TiCl(2) with NaOO(t)Bu in THF at -20 degrees C. Treatment of 1 with AgOTf at -20 degrees C gives the triflate complex Cp(2)Ti(OO(t)Bu)OTf (2), which is rapidly converted to the bromide Cp(2)Ti(OO(t)Bu)Br (3) on addition of (n)Bu(4)NBr. The X-ray crystal structures of 1 and 3 both show eta(1)-OO(t)Bu ligands. Complex 2 is stable only below -20 degrees C; (1)H, (13)C, and (19)F NMR spectra suggest that it also contains an eta(1)-OO(t)Bu ligand. Removal of the chloride from 1 with [Ag(Et(2)O)(2)]BAr'(4) (Ar' = 3,5-(CF(3))(2)C(6)H(3))) yields the etherate complex [Cp(2)Ti(OO(t)Bu)(OEt(2))]BAr'(4) (4). Again, coordination of a fourth ligand to the Ti center indicates an eta(1)-OO(t)Bu ligand in 4. These peroxide complexes do not directly oxidize olefins or phosphines. For instance, the cationic etherate complex 4 reacts with excess Et(3)P simply by displacement of the ether to form [Cp(2)Ti(eta(1)-OO(t)Bu)(Et(3)P)]BAr'(4) (5). Compounds 1-5 all decompose by O-O bond homolysis, based on trapping and computational studies. The lack of direct oxygen atom transfer reactivity is likely due to the eta(1) coordination of the peroxide and the inability to adopt more reactive eta(2) geometry. DFT calculations indicate that the steric bulk of the (t)Bu group inhibits formation of the hypothetical [Cp(2)Ti(eta(2)-OO(t)Bu)](+) species.     

Characterization of lithium sulfate as an unsymmetrical-valence salt bridge for the minimization of liquid junction potentials in aqueous-organic solvent mixtures

The transference numbers t of lithium sulfate in acetonitrile/water and methanol/water solvent mixtures have been studied by measuring the emfs of such transference cells as Pb(Hg)|PbSO(4)|Li(2)SO(4) (m(2))||Li(2)SO(4) (m(1))|PbSO(4)| Pb(Hg), Hg|Hg(2)SO(4)|Li(2)SO(4) (m(2))||Li(2)SO(4) (m(1))|Hg(2)SO(4)|Hg, and Li(x)Hg(1-)(x)|Li(2)SO(4) (m(1))||Li(2)SO(4) (m(2))|Li(x)Hg(1-)(x), in view of characterizing Li(2)SO(4) as an unsymmetrical salt bridge for the minimization of liquid junction potentials in potentiometric applications. In water, Li(2)SO(4) is nearly as good a salt bridge as the popular KCl one. Its effectiveness has been verified through the operational pH-metric cell using various aqueous pH(S) standards. In acetonitrile/water solvents of 0.09 mass fraction of acetonitrile at 298.15 K, Li(2)SO(4) shows exact ionic equitransference, obeying the general condition t(+)/z(+) = t(-)/|z(-)|. The Li(2)SO(4) salt bridge can be used either for simple insertion between two different electrolyte solutions to minimize the intervening liquid junction potentials, as the outer component of a double-bridge arrangement of any commonly available reference electrode, or, obviously, for structural incorporation in sulfate-reversible reference electrodes as the appropriate supporting and bridge electrolyte. The operational potential of the Hg| Hg(2)SO(4)|2 m Li(2)SO(4) reference electrode in aqueous solutions is 0.6326 V at 298.15 K.     

Electro-catalytic degradation of phenol on several metal-oxide anodes

Three kinds of Ti-based multilayer metal-oxide electrode, including Ti/SnO(2)+Sb(2)O(3)/PbO(2), Ti/SnO(2)+Sb(2)O(3)/MnO(x) and Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2) electrodes, were prepared by thermal decomposition, and SnO(2)+Sb(2)O(3) coatings were produced with a polymeric precursor method (PPM). The conversion of phenol was carried out with these electrodes as anodes under galvanostatic control. Samples during the electrolyses were characterized with UV-vis spectra and chromatography, and chemical oxygen demand (COD) and instantaneous current efficiency (ICE) for phenol degradation were also determined. The results show that phenol can be oxidized and degraded for all of the three anodes, and the oxidation reactions of phenol follow first-order kinetics, but there are considerable differences in the effectiveness and performance of electro-catalytic degradation. Phenol can be degraded relatively fast on the Ti/SnO(2)+Sb(2)O(3)/PbO(2) anode and the degradation rate of phenol is slower with the Ti/SnO(2)+Sb(2)O(3)/MnO(x) electrode, and the slowest with the Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2) electrode, whose apparent rate constants are 2.49 x 10(-2), 1.42 x 10(-2) and 9.76 x 10(-3) min(-1), respectively. The rates of electro-catalytic degradation relate to oxygen evolution potential, and the higher the oxygen evolution potential, the better the performance of electro-catalytic degradation. The potential for oxygen evolution at the Ti/SnO(2)+Sb(2)O(3)/PbO(2) anode is highest, then Ti/SnO(2)+Sb(2)O(3)/MnO(x), following Ti/SnO(2)+Sb(2)O(3)/RuO(2)+PbO(2). The accelerated life tests at 60 degrees C and in 1.0 mol L(-1) aqueous H(2)SO(4) with an anodic current density of 4.0 Acm(-2) show that the service life is prolonged when the SnO(2)+Sb(2)O(3) interlayer coating are inserted between Ti substrate and active layers.     

Dumbbell-like PtPd-Fe(3)O(4) Nanoparticles for Enhanced Electrochemical Detection of H(2)O(2)

Dumbbell-like Pt(x)Pd(100-x)-Fe(3)O(4) nanoparticles (NPs) were synthesized and studied for electrocatalytic reduction and sensing of H(2)O(2). In 0.1 M phosphate buffered saline (PBS) solution, the 4-10 nm Pt(x)Pd(100-x)-Fe(3)O(4) NPs showed the Pt/Pd composition-dependent catalysis with Pt(48)Pd(52)-Fe(3)O(4) NPs having the best activity. The Pt(48)Pd(52)-Fe(3)O(4) NPs were tested for H(2)O(2) detection, and their H(2)O(2) detection limit reached 5 nM, which was suitable for monitoring H(2)O(2) generated from Raw 264.7 cells. These dumbbell-like PtPd-Fe(3)O(4) NPs are the most sensitive probe ever reported and can be used to achieve real-time quantitative detection of H(2)O(2) in biological environment for biological and biomedical applications.