多核Nd-Al双金属配合物对丁二烯的聚合——Ⅱ.聚合的一般规律

在从均相稀土Ziegler-Natta催化剂中分离出有双烯聚合活性的Nd-Al双金属配合物的基础上,利用该配合物可在无助催化剂烷基铝存在下单独引发丁二烯聚合的特性,详细研究了活性体、外加烷基铝、单体浓度,温度及时间等变量对聚合的影响;对比了活性体引发聚合与一般Ziegler-Natta催化聚合在一般规律上的异同。以更客观的实验事实论证了烷基铝在聚合过程中的作用,通过聚合产物的GPC测定讨论了活性体聚合中存在的键转移反应,确认外加烷基铝的键转移能力最强。所得结果有助于对稀土催化定向聚合过程的深入了解。

由氯化稀土体系获得的Nd-Al双金属活性体的组成及其定向聚合活性

研究了从三氯化钕甲基磷酸二仲辛酯配合物(NdCl_3·3p_(350))与烷基铝(AlR_3)反应体系中分离出的Nd-A]双金属活性体的组成及其定向聚合活性。由Ndcl_3·3P_(350)-Al[(CH_2)_7-CH_3]_3及Al(C_2H_5)_3体系所得活性体的激光拉曼光谱发现,该活性体中存在稀土—碳键,可能的组成为Nd-(CH_2)_7CH_3及Nd-CH_2CH_3。这是稀土催化体系中存在稀土烷基化反应的直接证据。据此提出了一个可能的活性中心形成过程。实验结果表明,无需AlR_3存在,单独使用上述活性体即可引发双烯烃聚合,并具有较高的活性和高的定向性。

多核Nd-Al双金属配合物对丁二烯的聚合——Ⅰ.聚合物的分子量与微观结构间的关系及其聚合机理的讨论

在从均相稀土催化剂中分离出有聚合活性的Nd-Al双金属配合物的基础上,利用该配合物可单独引发丁二烯聚合的特点,较详细地研究了活性体浓度,外加烷基铝浓度,单体浓度以及聚合温度等因素对聚合产物分子量及微观结构的影响,确认二者之间存在着一定的内在联系,即分子量越高,顺式含量也越高;反之,分子量越低,顺式含量也越低。对此,本文提出了增长链对聚合过程起反作用的观点,从聚合机理的角度给予了解释。

稀土元素对二次锂电池中Li-Al负极材料电化学行为的影响

用纯锂作二次锂电池的负板材料有形成锂枝晶和钝化膜的缺点,采用在铝或其他金属如钙、镁、锡上欠电位沉积锂形成锂合金代替纯锂,对克服上述缺点有一定效果.本文报导了以稀土铝合金代替纯铝作基底欠电位沉积锂,在LiClO_4/碳酸丙烯酯电解液中稀土对改进电极性能有有益的影响.

Y-Al双金属稀土配合物的合成和晶体结构

稀土化合物和烷基铝反应的研究,不仅对揭示f轨道的本质且对阐明稀土配位催化聚合烯烃的催化剂结构都有重要意义。Grcco等曾报道C_8H_8Ce(μ-O-i-C_3H_7)_2Al(C_2H_5)_2配合物,但尚未见晶体结构数据。 本文介绍了一种新的Y-Al双金属配合物的合成和培养晶体的方法。用四圆衍射仪确定了它的晶体结构,并用~1H NMR、ESCA等方法研究了配合物中钇的价态。

Effects of starvation on larval growth, survival and metamorphosis of Ivory shell Babylonia formosae habei Altena et al., 1981 (Neogastropoda : Buccinidae)

The impact of starvation on larvae of Ivory shell Babylonia formosae habei was studied in a laboratory experiment. Newly hatched veligers showed considerable tolerance to starvation due to their endogenous yolk material, and time to the point-of-no-return (PNR; the threshold point during starvation after which larvae can longer metamorphose even if food is provided) was calculated to be 104.5 h. However, starvation still affected larval growth, survival, and metamorphosis. Mean shell length of larvae increased 49.77 mum day(-1) for nonstarved, but only 11.13 mum day (-1) for larvae starved for 108 h. After larvae began feeding, their growth rates rapidly recovered to the level of the nonstarved following short periods of starvation (less than 48 h), but were inhibited and unable to ever reach the level of the nonstarved when being starved beyond 48 h. Percent metamorphosis was 53.75% for the nonstarved, but all larvae died before 10 days for those starved for 108 h. Starvation not only affected larval time to reach metamorphosis, but also caused the delay in the time to metamorphosis. For the nonstarved, larvae took only 11.5 days to reach spontaneous metamorphosis, but they took 20 days to reach spontaneous metamorphosis when starved for 96 h, and this duration of delayed metamorphosis reached 8.5 days. Furthermore, the importance of yolk material for maintaining larval survival of B. formosae habei during starvation periods is also discussed. (C) 2004 Elsevier B.V. All rights reserved.

Grey interrelation analysis to assess the influence of elements on the galvanic efficiency of Al sacrificial anode

Grey interrelation analysis method was used to study the correlation of Al-anode elements and its galvanic efficiency at 20 degreesC, 40 degreesC and 60 degreesC. Twenty-eight kinds of Al-anodes were made for experiments by the method given by Chinese National Standard GB4948-85 [1] and the correlation degree of elements added in the anodes were calculated. The results showed that the order of elements affecting galvanic efficiency at different temperature is basically the same, and the correlation degree can reflect the variation of Al-anode galvanic efficiency when changing temperature. It is suggested that the elements being added in Al-anode are Zn, In, Ga, Mg.

Formation of nano-crystalline corrosion products on Zn-Al alloy coating exposed to seawater

Hot dip Zn-Al alloy coating performs better than hot dip galvanized coating and 55% Al-Zn-Si coating as well with regard to general seawater corrosion protection. A characterization of the corrosion products on Zn-Al alloy coating immersed in dynamic aerated seawater has been performed mainly based on transmission electron microscopy (TEM) for morphological analysis and X-ray diffraction (XRD) technique for crystalline phase identification. The XRD and TEM analyses showed that the corrosion products mainly were typical nanometer Zn4CO3(OH)(6).H2O, Zn-5(OH)(8)Cl-2 and Zn6Al2CO3(OH)(16). 4H(2)O microcrystals. This probably is connected to the co-precipitation of Zn2+ and Al3+ ions caused by adsorption. Zn-Al alloy coating being suffered seawater attacks, AI(OH)(3) gel was first produced on the coating surface. Zn and Al hydroxides would co-precipitate and form double-hydroxide when the concentration of adsorbed Zn2+ ions by the newly produced gel exceeded the critical degree of supersaturation of the interphase nucleation. However, because the growth of the crystals was too low to keep in step with the nucleation, a layer of nano-crystalline corrosion products were produced on the surface of the coating finally. (C) 2001 Elsevier Science Ltd. All rights reserved.

Study on growth factors of intermetallic layer within hot-dipped 25% Al-Zn alloy coating on steel

25%Al-Zn alloy coating performs better than hot dip galvanized coating and 55%Al-Zn-Si coating with regard to general seawater corrosion protection. This study deals with the interfacial intermetallic layer's growth, which affects considerably the corrosion resistance and mechanical properties of 25%Al-Zn alloy coatings, by means of three-factor quadratic regressive orthogonal experiments, The regression equation shows that the intermetallic layer thickness decreases rapidly with increasing content of Si added to the Zn-Al alloy bath, increases with rise in bath temperature and prolonging dip time. The most effective factor that determined the thickness of intermetallic layer was the amount of Si added to Zn-Al alloy bath, while the effect of bath temperature and dip time on the thickness of intermetallic layer were not very obvious.

Nicotinic acid as a nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings on steels in diluted hydrochloric acid

The inhibition effect of nicotinic acid for corrosion of hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid was investigated using quantum chemistry analysis, weight loss test, electrochemical measurement, and scanning electronic microscope (SEM) analysis. Quantum chemistry calculation results showed that nicotinic acid possessed planar structure with a number of active centers, and the populations of the Mulliken charge, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) were found mainly focused around oxygen and nitrogen atoms, and the cyclic of the benzene as well. The results of weight loss test and electrochemical measurement indicated that inhibition efficiency (IE%) increased with inhibitor concentration, and the highest inhibition efficiency was up to 96.7%. The corrosion inhibition of these coatings was discussed in terms of blocking the electrode reaction by adsorption of the molecules at the active centers on the electrode surface. It was found that the adsorption of nicotinic acid on coating surface followed Langmuir adsorption isotherm with single molecular layer, and nicotinic acid adsorbed on the coating surface probably by chemisorption. Nicotinic acid, therefore, can act as a good nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid solution. (c) 2007 Elsevier Ltd. All rights reserved.

NO reduction and CO oxidation over Cu/Ce/Mg/Al mixed oxide catalyst in FCC operation

Simultaneous NO reduction and CO oxidation in the presence of O-2,H2O and SO2 over Cu/Mg/AUO (Cu-cat), Ce/Mg/Al/O (Ce-cat) and Cu/Ce/Mg/Al/O (CuCe-cat) were studied. At low temperatures (<340 degreesC), the presence of O-2 or H2O enhanced the activity of CuCe-cat for NO and CO conversions, but significantly suppressed the activity of Cu-cat and Ce-cat, At high temperature (720 degreesC), the presence of O-2 or H2O had no adverse effect on the NO and CO conversions over these catalysts. The addition of SO2 to NO + CO + O-2 + H2O system had no effect on the, reaction of CO + O-2 over Cu-cat, but deactivated this catalyst for NO + CO and CO + H2O reactions; over Ce-cat, all of these reactions of NO + CO, CO + O-2 and CO + H2O were suppressed significantly; over CuCe-cat, NO + CO and CO + O-2 reactions were not affected while the reaction of CO + H2O was slightly inhibited. (C) 2002 Elsevier Science B.V. All rights reserved.