Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Environmentally benign Fe chelates in plant nutrition

The low solubility of iron (Fe) depresses plant growth in calcareous soils. In order to improve Fe availability, calcareous soils are treated with synthetic ligands, such as ethylenediaminetetraacetic acid (EDTA) and ethylenediimi-nobis(2-hydroxyphenyl)acetic acid (EDDHA). However, high expenses may hinder their use (EDDHA), and the recalcitrance of EDTA against biodegra-dation may increase the potential of cadmium (Cd) and lead (Pb) leaching. This study evaluated the ability of biodegradable ligands, i.e. different stereo-isomers of ethylenediaminedisuccinic acid (EDDS), to provide Fe for lettuce (Lactuca sativa L.) and ryegrass (Lolium perenne cv. Prego), their effects on uptake of other elements and solubility in soils and their subsequent effects on the activity of oxygen-scavenging enzymes in lettuce. Both EDTA and EDDHA were used as reference ligands. In unlimed and limed quartz sand both FeEDDS(S,S) and a mixture of stereo-isomers of FeEDDS (25% [S,S]-EDDS, 25% [R,R]-EDDS and 50% [S,R]/[R,S]-EDDS), FeEDDS(mix), were as efficient as FeEDTA and FeEDDHA in providing lettuce with Fe. However, in calcareous soils only FeEDDS(mix) was comparable to FeEDDHA when Fe was applied twice a week to mimic drip irrigation. The Fe deficiency increased the manganese (Mn) concentration in lettuce in both acidic and alkaline growth media, whereas Fe chelates depressed it. The same was observed with zinc (Zn) and copper (Cu) in acidic growth media. EDDHA probably affected the hormonal status of lettuce as well and thus depressed the uptake of Zn and Mn even more. The nutrient concentrations of ryegrass were only slightly affected by the Fe availability. After Fe chelate splitting in calcareous soils, EDDS and EDTA increased the solubility of Zn and Cu most, but only the Zn concentration was increased in lettuce. The availability of Fe increased the activity of oxygen-scavenging enzymes (ascorbate peroxidase, guaiacol peroxidase, catalase). The activity of Cu/ZnSOD (Cu/Zn superoxide dismutase) and MnSOD in lettuce leaves followed the concentrations of Zn and Mn. In acidic quartz sand low avail-ability of Fe increased the cobalt (Co) and nickel (Ni) concentrations in let-tuce, but Fe chelates decreased them. EDTA increased the solubility of Cd and Pb in calcareous soils, but not their uptake. The biodegradation of EDDS was not affected by the complexed element, and [S,S]-EDDS was biodegraded within 28 days in calcareous soils. EDDS(mix) was more recalcitrant, and after 56 days of incubation water-soluble elements (Fe, Mn, Zn, Cu, Co, Ni, Cd and Pb) corresponded to 10% of the added EDDS(mix) concentration.

Valence states and magnetic properties of LaNi1-xMnxO3 (for 0≤x≤0.2 and x=0.5)

Single-phase LaNi1-xMnxO3 samples in the compositional range 0nickel and manganese ions. X-ray absorption and XPS measurements indicate the presence of Mn(III) and Ni(III) valence states at room temperature for x=0.1, 0.2 and 0.5. Magnetic susceptibility data suggest Mn4+ solute ions and Stoner-enhanced Pauli paramagnetism of the metallic solvent for x=0.01 with a smooth transition to Mn3+ solute ions and a spontaneously magnetised solvent conduction band at x=0.05. Below 200K, the x=0.05 sample forms superparamagnetic clusters, and below 40K there is evidence for an antiferromagnet spin-density wave. Comparisons with LaCo0.95Mn0.05O3 and La0.98Sr0.02CoO3 confirm that the long-range magnetic coupling occurs via solvent electrons in a narrow conduction band. The conductivity changes from that of a narrow-band metal for x<0.01 to that more characteristic of diffusive motion for x>0.05, but any motional enthalpy appears to remain small ( Delta Hm approximately=0). The x=0.1 sample exhibits ferrimagnetic spin glass behaviour below 40K, and the ferromagnetic interactions increase with manganese concentration. The oxide with x=0.50 is ferromagnetic with a well defined Curie temperature.

Wear resistance of cast graphitic aluminium alloys

Wear rates of several cast aluminium base alloys have been measured for lubricated rubbing against a rotating hardened steel disk. Wear rates of cast graphitic aluminium-silicon-nickel alloys were lower than those of pure Al, Al-Si and Al-Si-Ni alloys especially above pressures of 0.02 kg/mm2. The high wear resistance is attributed to the presence of graphite particles in the matrix which act as a solid lubricant. Additions of nickel alone to Al-Si alloys decrease the wear resistance. Graphitic aluminium-silicon-nickel alloys containing above 2% graphite can be mated unlubricated against the rotating steel disk after a one minute lubricated run-in period. Graphite particles may be potentially suitable to replace part of all of the tin in aluminium-tin bearing alloys.

Effect of microstructure and mechanical properties on the seizure resistance of cast aluminium alloys

Seizure resistance of several cast aluminium base alloys has been examined using a standard Hohman Wear Tester. Disks of aluminium base alloys were run against a standard aluminium 12% silicon base alloy. The seizure resistance of the alloys (as measured by the lowest bearing parameter reached before seizure) increased with hardness, yield and tensile strength. In Al-Si-Ni alloys where silicon and nickel have little solid solubility in α-aluminium and Si and Ni Al3 hard phases are formed, the minimum bearing parameter decreased with the parameter V (The product of vol. % of hard phases in the disk and the shoe). Apparently the silicon and NiAl3 particles provided discontinuities in the matrix and reduced the probability (1 − V) of the α-aluminium phase in the disk coming into contact with the α-aluminium phase in the shoe. The copper and magnesium containing Al-Si-Ni alloys with lesser volumes of hard phases exhibit considerably better seizure resistance indicating that a slight increase in the solute content or the hardness of the primary α-phase leads to a considerable increase in seizure resistance. Deformation during wear and seizure leads to fragmentation of the original hard particles into considerably smaller particles uniformly dispersed in the deformed α-aluminium matrix.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

Wear resistance of cast graphitic aluminium alloys

Wear rates of several cast aluminium base alloys have been measured for lubricated rubbing against a rotating hardened steel disk. Wear rates of cast graphitic aluminium-silicon-nickel alloys were lower than those of pure Al, Al-Si and Al-Si-Ni alloys especially above pressures of 0.02 kg/mm2. The high wear resistance is attributed to the presence of graphite particles in the matrix which act as a solid lubricant. Additions of nickel alone to Al-Si alloys decrease the wear resistance. Graphitic aluminium-silicon-nickel alloys containing above 2% graphite can be mated unlubricated against the rotating steel disk after a one minute lubricated run-in period. Graphite particles may be potentially suitable to replace part of all of the tin in aluminium-tin bearing alloys.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

ESR study of copper diethyldithiophosphate

ESR investigations are reported in single crystals of copper diethyldithiophosphate, magnetically diluted with the corresponding diamagnetic nickel complex. The spectrum at normal gain shows hyperfine components from 63Cu, 65Cu, and 31P nuclei. At much higher gain, hyperfine interaction from 33S nuclei in the ligand is detected. The spin Hamiltonian parameters relating to copper show tetragonal symmetry. The measured parameters are g = 2.085, g =2.025, A63Cu = 149.6 × 10−4 cm−1, A65Cu = 160.8 × 10−4 cm−1, BCu = 32.5 × 10−4 cm−1 and QCu 5.5 × 10−4cm−1. The 31P interaction is isotropic with a coupling constant AP = 9.6 × 10−4 cm−1. Angular variation of the 33S lines shows two different hyperfine tensors indicating the presence of two chemically inequivalent Cu S bonds. The experimentally determined hyperfine constants are A =34.9×10−4 cm−1, B =26.1×10−4 cm−1, A =60.4×10−4 cm−1, B =55.5×10−4 cm−1. The hyperfine parameters show that the hybridization of the ligand orbitals is very sensitive to the symmetry around the ligand. The g values and Cu hyperfine parameters are not much affected by the distortions occurring in the ligand. The energies of the d-d transitions are determined by optical absorption measurements on Cu diethyldithiophosphate in solution. Using the spin Hamiltonian parameters together with optical absorption results, the MO parameters for the complex are calculated. It is found that in addition to the bond, the bonds are also strongly covalent. ©1973 The American Institute of Physics

Liquid phase hydrogenation of aniline in a trickle bed reactor

A rate equation is developed for the liquid phase hydrogenation of aniline over cylindrical catalyst pellets of 30% nickel deposited on clay in a trickle bed reactor. The equation takes into account external and internal diffusional limitations, and describes the experimental data adequately. The hydrogenation reaction is first order with respect to hydrogen and zero order with respect to aniline. Effectiveness factors are in the range 0.003-0.03. Apparent activation energy of the reaction is 12.7 kcal/mol and true activation energy is 39.6 kcal/mol.

Production of cast aluminium-graphite particle composites using a pellet method

Copper- and nickel-coated graphite particles can be successfully introduced into aluminium-base alloy melts as pellets to produce cast aluminium-graphite particle composites. The pellets were made by pressing mixtures of nickel- or copper-coated graphite particles and aluminium powders together at pressures varying between 2 and 20 kg mm–2. These pellets were dispersed in aluminium alloy melts by plunging and holding them in the melts using a refractory coated mild steel cone, until the pellets disintegrated and the powders were dispersed. The optimum pressure for the preparation of pellets was 2 to 5 kg mm–2 and the optimum size and percentage of aluminium powder were 400 to 1000mgrm and 35 wt% respectively. Under optimum conditions the recovery of the graphite particles in the castings was as high as 96%, these particles being pushed into the last freezing interdendritic regions. The tensile strength and the hardness of the graphite aluminium alloys made using the pellet method are comparable to those of similar composites made using gas injection or the vortex method. The pellet method however has the advantage of greater reproducibility and flexibility. Dispersion of graphite particles in the matrix of cast aluminium alloys using the pellet method increases their resistance to wear.

ESR study of copper diethyldithiophosphate

ESR investigations are reported in single crystals of copper diethyldithiophosphate, magnetically diluted with the corresponding diamagnetic nickel complex. The spectrum at normal gain shows hyperfine components from 63Cu, 65Cu, and 31P nuclei. At much higher gain, hyperfine interaction from 33S nuclei in the ligand is detected. The spin Hamiltonian parameters relating to copper show tetragonal symmetry. The measured parameters are g|| = 2.085, g[perpendicular]=2.025, A63Cu = 149.6 × 10−4 cm−1, A65Cu = 160.8 × 10−4 cm−1, BCu = 32.5 × 10−4 cm−1 and QCu [infinity] 5.5 × 10−4cm−1. The 31P interaction is isotropic with a coupling constant AP = 9.6 × 10−4 cm−1. Angular variation of the 33S lines shows two different hyperfine tensors indicating the presence of two chemically inequivalent Cu[Single Bond]S bonds. The experimentally determined hyperfine constants are A ₁^s=34.9×10−4 cm−1, B ₁^s=26.1×10−4 cm−1, A ₂^s=60.4×10−4 cm−1, B₂^s=55.5×10−4 cm−1. The hyperfine parameters show that the hybridization of the ligand orbitals is very sensitive to the symmetry around the ligand. The g values and Cu hyperfine parameters are not much affected by the distortions occurring in the ligand. The energies of the d-d transitions are determined by optical absorption measurements on Cu diethyldithiophosphate in solution. Using the spin Hamiltonian parameters together with optical absorption results, the MO parameters for the complex are calculated. It is found that in addition to the sigma bond, the pi bonds are also strongly covalent. ©1973 The American Institute of Physics.

Fabrication and mechanisms of densification of ZrB2-based ultra high temperature ceramics by reactive hot pressing

Dense ZrB2-SiC (25-30 vol%) composites have been produced by reactive hot pressing using stoichiometric Zr, B4C, C and Si powder mixtures with and without Ni addition at 40 MPa, 1600 degrees C for 60 min. Nickel, a common additive to promote densification, is shown not to be essential; the presence of an ultra-fine microstructure containing a transient plastic ZrC phase is suggested to play a key role at low temperatures, while a transient liquid phase may be responsible at temperatures above 1350 degrees C. Hot Pressing of non-stoichiometric mixture of Zr, B4C and Si at 40 MPa, 1600 degrees C for 30 min resulted in ZrB2-ZrCx-SiC (15 vol%) composites of similar to 98% RD.

A fluctuation-based characterization of athermal phase transitions:Application to shape memory alloys

We employ a fluctuation-based technique to investigate the athermal component associated with martensite phase transition, which is a prototype of temperature-driven structural transformation. Statistically, when the phase transition is purely athermal, we find that the temporal sequence of avalanches under constant drive is insensitive to the drive rate. We have used fluctuations in electrical resistivity or noise in nickel titanium shape memory alloys in three different forms: a thin film exhibiting well-defined transition temperatures,a highly disordered film, and a bulk wire of rectangular cross-section. Noise is studied in the realm of dynamic transition,viz.while the temperature is being ramped, which probes into the kinetics of the transformation at real time scales,and could probably stand out as a promising tool for material testing in various other systems, including nanoscale devices.

Thermal properties of single-phase Y2SiO5

Y2SiO5 is a promising candidate for oxidation-resistant or environmental/thermal barrier coatings (ETBC) due to its excellent high-temperature stability, low elastic modulus and low oxygen permeability. In this paper, we investigated the thermal properties of Y2SiO5 comprehensively, including thermal expansion, thermal diffusivity, heat capacity and thermal conductivity. It is interesting that Y2SiO5 has a very low thermal conductivity (∼1.40 W/m K) but a relatively high linear thermal expansion coefficient ((8.36 ± 0.5) × 10-6 K-1), suggesting compatible thermal and mechanical properties to some non-oxide ceramics and nickel superalloys as ETBC layer. Y2SiO5 is also an ideal EBC on YSZ TBC layer due to their close thermal expansion coefficients. As a continuous source of Y3+, it is predicted that Y2SiO5 EBC may prolong the lifetime of zirconia-based TBC by stopping the degradation aroused by the loss of Y stabilizer.