阴极电泳涂装技术的发展

在扼要分析阴极电泳涂装原理的基础上，重点介绍了阴极电泳涂料的组成及其发展趋势，探讨了前处理及电泳工艺参数对阴极电泳质量的影响，并展望了阴极电泳涂装技术发展的方向。     

阴极电泳涂装工艺在微型轿车上的应用

系统介绍了微型轿车阴极电泳涂装的主要工艺和设备，讨论了涂层质量的影响因素，并指出了阴极电泳涂装需注意的几个问题。     

自泳涂装工艺及应用

自泳涂装是通过化学反应在钢铁基材表面形成漆膜的一种涂装方式.介绍了自泳涂装的反应机理及涂装工艺,通过与阴极电泳的比较分析了自泳涂装的漆膜性能及优缺点,认为自泳涂装可在一定范围内替代阴极电泳.     

汽车车身阴极电泳涂装工艺控制要点

论述了电泳涂装前处理、电泳涂装、电泳后清洗、电泳涂膜的烘干等汽车车身阴极电泳涂装工艺及正常生产时阴极电泳涂装生产现场和电泳槽液的控制要点.     

汽车车架阴极电泳涂装的工艺与设备

以一条汽车车架阴极电泳涂装的自行小车输送涂装生产线为例,论述了涂装前未除锈、未除去氧化皮的汽车车架阴极电泳涂装生产线的工艺处理过程和条件,提出了车架表面氧化皮的超声波酸洗除锈工艺;阐述了生产线的设备选型原则、设备组成和布置;探讨了生产线设计方面应注意的问题.     

炮弹、汽车雨刮器等中小工件阴极电泳涂装生产线设计

详细论述了炮弹、汽车雨刮器等中小工件阴极电泳涂装生产线的工艺设计,阐述了生产线的基本型式、设备组成和设计原则,介绍了一种新型的针对中小工件阴极电泳涂装的步进直线式T型行车输送涂装生产线.     

厚膜阴极电泳涂料在轿车零部件上的涂装

介绍了轿车零部件对电泳涂装的要求及ＨＥＤ－Ｉ型阴极电泳涂料的主要性能指标,讨论了前处理、涂装线、电泳工艺参数控制及后处理对涂装质量的影响,并对目前轿车零部件涂装中存在的问题进行了初步探讨。     

电泳涂装技术问答（1）

电泳涂装技术问答（１）中国第一汽车集团公司（１３００１１）王锡春［编者按］作者在中国第一汽车制造厂从事电泳涂装技术的开发、应用近３０年，根据自身实践经验和收集的资料，并以近１０年来国内汽车工业普遍采用的阴极电泳为主题，编写了电泳涂装技术７２问，以科普...     

电泳涂装设备对涂装质量的影响

论述了电泳设备在涂装中的重要性，主要论述了阴极罩及虎系统对涂层质量的影响。     

阴极电泳涂装的管理

阴极电泳涂装的管理广西省柳州市钢圈厂（５４５００７）莫京辉阴极电泳涂装越来越受人们青睐，最根本的原因是涂膜质量较好，好的涂膜质量除了与涂料种类、品质有关外，还与泳徐生产中的科学管理密切相关。本文就此谈一些体会。１涂膜质量１．１严格检验涂料涂料除了种类...     

Chromium and zinc uptake by algae Gelidium and agar extraction algal waste: kinetics and equilibrium

Biosorption of chromium and zinc ions by an industrial algal waste, from agar extraction industry has been studied in a batch system. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction, and the industrial waste immobilized with polyacrylonitrile (composite material). Langmuir and Langmuir-Freundlich equilibrium models describe well the equilibrium data. The parameters of Langmuir equilibrium model at pH 5.3 and 20 degrees C were for the algae, q(L)=18 mg Cr(III)g(-1) and 13 mgZn(II)g(-1), K(L) = 0.021l mg(-1)Cr(III) and 0.026l mg(-1) Zn(II); for the algal waste, q(L)=12 mgCr(III)g(-1) and 7mgZn(II)g(-1), K(L)=0.033lmg(-1) Cr(III) and 0.042l mg(-1) Zn(II); for the composite material, q(L) = 9 mgCr(III)g(-1) and 6 mgZn(II)g(-1), K(L)=0.032l mg(-1)Cr(III) and 0.034l mg(-1)Zn(II). The biosorbents exhibited a higher preference for Cr(III) ions and algae Gelidium is the best one. The pseudo-first-order Lagergren and pseudo-second-order models fitted well the kinetic data for the two metal ions. Kinetic constants and equilibrium uptake concentrations given by the pseudo-second-order model for an initial Cr(III) and Zn(II) concentration of approximately 100 mgl(-1), at pH 5.3 and 20 degrees C were k(2,ads)=0.04 g mg(-1)Cr(III)min(-1) and 0.07 g mg(-1)Zn(II)min(-1), q(eq)=11.9 mgCr(III)g(-1) and 9.5 mgZn(II)g(-1) for algae; k(2,ads)=0.17 g mg(-1)Cr(III)min(-1) and 0.19 g mg(-1)Zn(II)min(-1), q(eq)=8.3 mgCr(III)g(-1) and 5.6 mgZn(II)g(-1) for algal waste; k(2,ads)=0.01 g mg(-1)Cr(III)min(-1) and 0.18 g mg(-1)Zn(II)min(-1), q(eq)=8.0 mgCr(III)g(-1) and 4.4 mgZn(II)g(-1) for composite material. Biosorption was modelled using a batch adsorber mass transfer kinetic model, which successfully predicts Cr(III) and Zn(II) concentration profiles. The calculated average homogeneous diffusivities, D(h), were 4.2 x 10(-8), 8.3 x 10(-8) and 1.4 x 10(-8)cm(2)s(-1) for Cr(III) and 4.8 x 10(-8), 9.7 x 10(-8) and 6.2 x 10(-8)cm(2)s(-1) for Zn(II), respectively, for Gelidium, algal waste and composite material. The algal waste has the lower intraparticle resistance.     

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.     

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.     

Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes

Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe(2)R')(Pyr)(2)(bipy) (1a-1g; R = 2,6-i-Pr(2)C(6)H(3) (Ar), adamantyl (Ad), 2,6-Me(2)C(6)H(3) (Ar'), 2-i-PrC(6)H(4) (Ar(iPr)), 2-ClC(6)H(4) (Ar(Cl)), 2-t-BuC(6)H(4) (Ar(t) (Bu)), and 2-MesitylC(6)H(4) (Ar(M)), respectively; R' = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans and two possible cis pyrrolide isomers of syn alkylidenes. Sonication of a mixture containing 1a-1g, HMTOH (2,6-dimesitylphenol), and ZnCl(2)(dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe(2)R')(Pyr)(OHMT) (3a-3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a-3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to formation of imido alkylidyne complexes of the type Mo(NR)(CCMe(2)R')(Me(2)Pyr)(bipy) (Me(2)Pyr = 2,5-dimethylpyrrolide; 4a - 4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe(2)Ph)(Pyr)(2)(bipy) (1a), Mo(NAr(iPr))(CHCMe(2)Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe(2)Ph)(Me(2)Pyr)(bipy) (4a), and Mo(NAr(T))(CCMe(3))(Me(2)Pyr)(bipy) (Ar(T) = 2-(2,4,6-i-Pr(3)C(6)H(2))C(6)H(4); 4g) showed structures with the normal bond lengths and angles.     

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.     

Mechanistic Investigation of Cycloreversion/Cycloaddition Reactions between Zirconocene Metallacycle Complexes and Unsaturated Organic Substrates

Treatment of the diazametallacycle Cp(2)Zr(N(t-Bu)C=N(SiMe(3))N(SiMe(3))) (4a) with diphenylacetylene resulted in the formation of the azametallacyclobutene Cp(2)Zr(N(t-Bu)C(Ph)=C(Ph)) (6a) and Me(3)SiN=C=NSiMe(3) in high yield. A kinetic study using UV-vis spectroscopy was carried out on the transformation. Saturation kinetic behavior was observed for the system, which is supportive of a mechanism that involves a reversible formal [2 + 2] retrocycloaddition of 4a to generate the transient imido species Cp(2)Zr=N-t-Bu (7a) and Me(3)-SiN=C=NSiMe(3). Trapping 7a with diphenylacetylene in an overall [2 + 2] cycloaddition reaction affords zirconacycle 6a. The study of cycloreversion/cycloaddition reactions between diazametallacycle complexes and diphenylacetylene was extended to other zirconocene systems. Detailed kinetic studies were performed for the exchange reactions between the diazametallacycle complexes Cp(2)Zr(N(2,6-Me(2)Ph)C=N(SiMe(3))N(SiMe(3))) (8a) and Cp(2)Zr-(N(2,6-Me(2)Ph)C=N(t-Bu)N(t-Bu)) (8b) with diphenylacetylene (5a) to give the corresponding azametallacyclobutene complex Cp(2)Zr(N(2,6-Me(2)Ph)C(Ph)=C(Ph)) (6c) and extruded carbodiimides (Me(3)SiN=C=NSiMe(3) for 8a and (t-Bu)N=C=N(t-Bu) for 8b). For both systems, the reactions were found to be first order in metallacycle and zero order in alkyne. Treatment of the diazametallacycle complexes Cp(2)Zr(N(2,6-i-Pr(2)Ph)C=N(Cyc)N(Cyc)) (9a) and Cp(2)Zr-(N(2,6-i-Pr(2)Ph)C=N(i-Pr(2))N(i-Pr(2))) (9b) with alkyne 5a resulted in the formation of the six-membered zirconacycles 10a,b, respectively, upon heating at 75 degrees C. The products 10a,b are generated from the overall insertion of alkyne 5a into the nitrogen-carbon bond of the zirconium-containing diazacyclobutane. Complex 10a has been characterized by an X-ray crystallographic study. When the azacyclobutene Cp(2)Zr(N(2,6-i-Pr(2)Ph)C(Ph)=C(Ph)) (6e) was treated with CycN=C=NCyc or (i-Pr)N=C=N(i-Pr), the same six-membered zirconacycle complexes 10a,b were obtained. Kinetic analysis of the reaction of 6e and (i-Pr)N=C=N(i-Pr) to yield 10b supports an associative process wherein alkyne 5a directly inserts into the zirconium-carbon bond of 6e. The diazametallacycle complex 4a underwent a stoichiometric metathetical exchange with symmetrical carbodiimides RN=C=NR (R = p-Tol, m-Tol, i-Pr, Cyc) to generate new cyclic zirconocene complexes and Me(3)SiN=C=NSiMe(3). Kinetic studies were carried out on the exchange reaction between 4a and (m-Tol)N=C=N(m-Tol) to form 4e and Me(3)SiN=C=NSiMe(3). The experimental rate data obtained are consistent with a dissociative mechanism. Additionally, the saturation rate constant derived for this system from the data is the same (within experimental error) as the saturation rate constant obtained from the kinetic study of 4a and diphenylacetylene to form 6a and Me(3)SiN=C=NSiMe(3). These findings provide additional support for a dissociative mechanistic pathway in the exchange reactions, since the rate constant in the formal [2 + 2] retrocycloaddition reaction to generate imidozirconocene species Cp(2)Zr=N-t-Bu (7a) and Me(3)SiN=C=NSiMe(3) should be the same for both reactions.     

Analysis of isotopic CO(2) mixtures by laser photoacoustic spectroscopy

Photoacoustic spectroscopic studies on a mixture of six CO(2) isotopes ((12) C(16) O(2), (12) C(18) O(2), (13) C (16) O(2), (13) C(18) O(2), (16) O(12) C(18) O, and (16) O(13) C(18) O) in the wavelength range of 9-11 mum by use of a home-built high-pressure continuously tunable CO(2) laser with a bandwidth of 0.017 cm(-1) are discussed. The concentrations of all CO(2) isotopes present in the mixture could be determined with good accuracy. Furthermore, the previously unknown absorption cross sections of some important lines of the(12) C(18) O(2), (13) C(18) O(2), and (16)O (13) C(18) O isotopes in the 9-11-mum range are reported.     

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.     

Physical and chemical modification of distillery sludge for Pb(II) biosorption

The waste distillery sludge from sugar-cane industry was pretreated physically (boiled, heated and autoclaved) as well as chemically (HCl, H(2)SO(4), H(3)PO(4), NaOH, Ca(OH)(2), Al(OH)(3), C(6)H(6), HCHO, CH(3)OH and C1(2)H(25)OSO(3)Na (sodium dodecyl sulphate (SDS)) for assessing the comparative sorption capacity of untreated and modified distillery sludge for Pb(II) biosorption from aqueous solutions. Experiments were conducted in shake flasks on a batch basis to access the effect of different experimental parameters such as pH, biosorbent dosage, biosorbent size, initial Pb(II) concentration and contact time. The uptake capacity 'q' (mg/g) of untreated and pretreated distillery sludge was in following order: NaOH (51.29+/-1.21)>HCl (49.82+/-1.22)>HCHO (49.56+/-1.14)>H(2)SO(4) (47.71+/-1.20)>HgCl(2) (45.32+/-1.06)>Ca(OH)(2) (44.01+/-1.18)>MeOH (43.73+/-1.23)>C(6)H(6) (42.72+/-1.19)>H(3)PO(4) (42.01+/-1.17)>SDS (40.87+/-1.27)>autoclaved (40.23+/-1.24)>Boiled (39.95+/-1.19)>heated (38.87+/-1.32)>Al (OH)(3) (38.30+/-1.14)>untreated (37.76+/-1.21). In further parameter studies, the optimized biosorbent size was 0.250 mm at pH 5 and best dose was 0.05 g of biosorbent. The applicability of the Langmuir and Freundlich models for sorption process was tested and best fitted model was Langmuir with the coefficient of determination (R(2)) value, 0.97, the process followed second order kinetic mechanism.     

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.