Chemical composition of “AKD vapour” and its implication to AKD vapour sizing

Alkyl ketene dimer (AKD) sizing of paper involves the redistribution of the wax over the fibre surface upon heating. The two major mechanisms widely studied so far are the spreading of an autophobic precursor of molten AKD and AKD vapour transport and re-deposition on the fibre surface. All previous work assumed that the transport of AKD vapour could be expressed by the change of water contact angle with substrates that were exposed to the vapour. Information regarding the chemical composition of the vapour phase above the AKD wax has not been found in the literature. In this work, a simple method for analysing the chemical composition of the vapour is established. Our preliminary results indicated that the chemical composition of AKD vapour in the temperature range of 75–80 °C is dominantly fatty acids. This suggests that the sizing effect by actual AKD molecules via the vapour deposition mechanism is likely to be insignificant in this temperature range. This also implies that fatty acids play a positive role in AKD sizing. The chemical stability of AKD in this temperature range is also studied.     

Synthesis and characterization of Cu,Ni and Zn binding capability of some amino- and imidazole hydroxamic acids: Effects of substitution of side chain amino-N for imidazole-N or hydroxamic-N-H for -N-CH3 on metal complexation

Solution equilibrium studies on Cu(II)-, Ni(II)- and Zn(II)-N-Me-β-Alaninehydroxamic acid (N-Me-β-Alaha), -N-Me-α-alaninehydroxamic acid (N-Me-α-Alaha), -Imidazole-4-carbohydroxamic acid (Im-4-Cha), -N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha) and -Imidazole-4-acetohydroxamic acid (Im-4-Aha) systems have been performed by pH-potentiometry, UV–Vis spectrophotometry, EPR, CD, ESI-MS and ¹H NMR methods. According to the results: (i) the amino-N atoms are more basic in N-Me-α-Alaha and N-Me-β-Alaha than the hydroxamate function, but the trend is just the opposite between the imidazole-N(3) and hydroxamate. (ii) The metal ion anchor is always the hydroxamate part in the amino acid derivatives, while it is always the imidazole-N(3) in the studied imidazolehydroxamic acids. (iii) The three studied N-Me derivatives do not form metallacrowns. Only hydroxamate type chelate is formed with N-Me-β-Alaha, but with N-Me-α-Alaha a new type of coordination mode (via amino-N and hydroxamate-O) also exists. N-Me-Im-4-Cha also forms a dinuclear complex, [M₂L₃], with Cu(II) and Ni(II) (but not with Zn(II)). In this complex, one of the three ligands might bridge the two metal ions (five-membered hydroxamate-(O,O) plus five-membered (N_im, O_carb) bridging bis-chelating mode), while each of the additional two ligands binds to one metal. (iv) The two studied N–H derivatives, having dissociable proton on the hydroxamic-N, are able to form metallacrown species. A pentanuclear complex, [M₅L₄H₋₄], is exclusively formed above pH 4 between Cu(II) and Im-4-Aha. Interestingly, this 12-metallacrown-4 type complex, although together with various mononuclear binding isomers, appears also with Ni(II) and Zn(II). Unfortunately, the complexes of Im-4-Cha are not soluble in water at physiological pH at all.     

Synthesis and X-ray structural study of octa-coordinated hexafluoroacetylacetone hafnium(IV) complex

Hexafluoroacetylacetonate hafnium(IV) complex has been synthesized and studied by X-ray structural analysis. Crystal data for C₃₀H₈F₃₆Hf₂O₁₄ are: a = 12.957(3) Å, b = 16.687(3) Å, c = 12.398(3) Å, β = 108.97°, space group P2₁/c, Z = 2, d _calc = 2.137 g/cm³, R = 0.047. The molecular structure is built from discrete binuclear molecules of Hf₂(OH)₂(hfac)₆ composition; the Hf...Hf distance in dimer is 3.533 Å. The structural units are connected by van der Waals interactions in the crystal.     

Crystal structure of oxotitanium(IV) 2,2,6,6-tetramethyl-3,5-heptanedionate

The structure of titanyl dipivalylmethanate TiO(dpm)₂ has been studied by X-ray diffraction analysis. The compound has a molecular structure formed by isolated centrosymmetrical dimers [TiO(dpm)₂]₂; the unit cell contains two structurally related, crystallographically unique binuclear molecules. The Ti...Ti distance in the dimer is 2.73 Å. Crystal data for Ti₂C₃₆H₇₆O₁₀: a = 32.477(6) Å, b = 14.409(3) Å, c = 25.630(5) Å; β = 107.82(3)°, space group C2/c, Z = 8, d _calc = 1.002 g/cm³.     

废水中偏二甲肼在Ni/Fe催化剂上的催化分解研究

研究了Ni/Fe催化剂对废水中偏二甲肼臭氧化分解的催化作用,考察了组分含量、体系的pH值和偏二甲肼初始浓度对催化反应的影响.结果表明,Ni/Fe催化剂对水中偏二甲肼的臭氧化具有良好的催化活性.催化剂组分含量、体系的pH值和初始浓度对反应的影响程度不大.对催化剂的XRD表征结果表明,催化剂主要由尖晶石结构的铁酸盐和FeNi3合金相组成,催化剂的良好催化性能与催化剂中尖晶石结构的铁酸盐和FeNi3合金相的形成有关.     

K-La-Ni/Si-2催化低碳烷烃与二氧化碳重整制合成气(英文)

Ｎｉ／Ｓｉ２催化剂具有较好的低碳烷烃与二氧化碳重整制合成气的反应性能，添加Ｌａ２Ｏ３助剂和Ｋ２Ｏ助剂可提高催化剂活性和合成气收率，从而进一步改善催化剂的低碳烷烃与ＣＯ２重整制合成气的反应性能，研制的ＫＬａＮｉ／Ｓｉ２催化剂，用于天然气与ＣＯ２重整反应制合成气可达９７％的低碳烷烃转化率和９５％以上的合成气收率。     

油溶性金属Ni纳米微粒的制备与表征

纳米材料的制备、性能与应用已成为近年来的研究热点之一犤１犦。由于在催化、光学和电学材料中的广泛应用，超细单分散的金属微粒的制备与性质已引起人们的广泛兴趣。通常制备金属纳米微粒的方法有两种：一是把固体金属材料分裂为纳米尺寸的颗粒，如机械粉碎、电弧放电及金属原子蒸气沉积犤２犦，用这种方法制备的金属微粒粒径一般都比较大，且粒子尺寸分布宽，另一种是把金属原子制成纳米尺度的颗粒，如乳液聚合法犤３犦、热解犤４犦、γ－射线辐照犤５犦、脉冲电沉积犤６犦和化学还原犤７犦等，这种方法制备的微粒粒径通常分布窄且粒子小…     

Model studies of the chemisorption of hydrogen and oxygen on nickel surfaces

Atomic chemisorption of hydrogen and oxygen on the Ni(100) surface has been studied using an Effective Core Potential (ECP) approach described in a previous paper. Clusters of up to 50 nickel atoms have been used to model the surface. The computed chemisorption energies are 62 kcal/mol (exp. 63 kcal/mol) for hydrogen and 106 kcal/mol (exp. 115–130 kcal/mol) for oxygen. Correlating the adsorbate and the cluster-adsorbate bonds is extremely important for obtaining accceptable results, particularly for oxygen. Reasonable convergence of chemisorption energies is obtained with 40–50 cluster atoms for both hydrogen and oxygen. For hydrogen the addition of a third cluster layer stabilizes the results considerably. Both hydrogen and oxygen are adsorbed at (or close to) the four-fold hollow site. The calculated barriers for surface migration are also in good agreement with the experimental estimates. The calculated equilibrium heights above the surface are on the other hand too high compared with experiments. This disagreement is believed to be due to core-valence correlation effects, which are not incorporated in the present ECP. The cluster convergence for the height above the surface is much slower than for the chemisorption energy.     

Assessing the biocompatibility of NiTi shape memory alloys used for medical applications

The present paper reviews aspects related to the biocompatibility of NiTi shape memory alloys used for medical applications. These smart metallic materials, which are characterised by outstanding mechanical properties, have been gaining increasing importance over the last two decades in many minimal invasive surgery and diagnostic applications, as well as for other uses, such as in orthodontic appliances. Due to the presence of high amounts of Ni, the cytotoxicity of such alloys is under scrutiny. In this review paper we analyse work published on the biocompatibility of NiTi alloys, considering aspects related to: (1) corrosion properties and the different methods used to test them, as well as specimen surface states; (2) biocompatibility tests in vitro and in vivo; (3) the release of Ni ions. It is shown that NiTi shape memory alloys are generally characterised by good corrosion properties, in most cases superior to those of conventional stainless steel or Co–Cr–Mo-based biomedical materials. The majority of biocompatibility studies suggest that these alloys have low cytotoxicity (both in vitro and in vivo) as well as low genotoxicity. The release of Ni ions depends on the surface state and the surface chemistry. Smooth surfaces with well-controlled structures and chemistries of the outermost protective TiO₂ layer lead to negligible release of Ni ions, with concentrations below the normal human daily intake.     

A New Hydroxo‐bridged Chromium(III) Dimer [Cr(saltn)OH]2·4H2O: Synthesis,Crystal Structure and Magnetic Properties

A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]₂·4H₂O [H₂saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr₂O₂ unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S₁=S₂=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm^‐1, and zJ' =0.18(3)cm^‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex.