Lithium-aluminium casting alloys and their associated metal-mould reactions

Aluminium - lithium alloys are specialist alloys used exclusively by the aerospace industry. They have properties that are favourable to the production of modern military aircraft. The addition of approximately 2.5 percent lithium to aluminium increases the strength characteristics of the new alloys by 10 percent. The same addition has the added advantage of decreasing the density of the resulting alloy by a similar percentage. The disadvantages associated with this alloy are primarily price and castability. The addition of 2.5 weight percent lithium to aluminium results in a price increase of 100% explaining the aerospace exclusivity. The processability of the alloys is restricted to ingot casting and wrought treatment but for complex components precision casting is required. Casting the alloys into sand and investment moulds creates a metal - mould reaction, the consequences of which are intolerable in the production of military hardware. The primary object of this project was to investigate and characterise the reactions occurring between the newly poured metal and surface of the mould and to propose a method of counteracting the metal - mould reaction. The constituents of standard sand and investment moulds were pyrolised with lithium metal in order to simplify the complex in-mould reaction and the products were studied by the solid state techniques of powder X-Ray diffraction and magic angle spinning nuclear magnetic resonance spectroscopy. The results of this study showed that the order of reaction was: Organic reagents> > Silicate reagents> Non silicate reagents Alphaset and Betaset were the two organic binders used to prepare the sand moulds throughout this project. Studies were carried out to characterise these resins in order to determine the factors involved in their reaction with lithium. Analysis revealed that during the curing process the phenolic hydroxide groups are not reacted out and that a redox reaction takes place between these hydroxides and the lithium in the molten alloys. Casting experiments carried out to assess the protection afforded by various hydroxide protecting agents showed that modern effective, protecting chemicals such as bis-trimethyl silyl acetamide and hexamethyldisilazane did not inhibit the metal - mould reaction to a sufficiently high standard and that tri-methylchlorosilane was consistently the best performer. Tri-methyl chlorosilane has a simple functionalizing mechanism compared to other hydroxide protecting reagents and this factor is responsible for its superior inhibiting qualities. Comparative studies of 6Li and 7Li N.M.R. spectra (M.A.S. and `off angle') establish that, for solid state (and even solution) analytical purposes 6Li is the preferred nucleus. 6Li M.A.S.N.M.R. spectra were obtained for thermally treated laponite clay. At temperatures below 800oC both dehydrated and rehydrated samples were considered. The data are consistent with mobility of lithium ions from the trioctahedral clay sites at 600oC. The superior resolution achievable in 6Li M.A.S.N.M.R. is demonstrated in the analysis of a microwave prepared lithium exchanged clay where 6Li spectroscopy revelaed two lithium sites in comparison to 7Li M.A.S.N.M.R. which gave only a single lithium resonance.

The mechanisms of melt stabilisation of polyolefins

The effects of melt stabilisers on the oxidative degradation of polyolefins (polypropylene, low density polyethylene) have been studied under a variety of processing conditions . The changes in the both chemical and physical properties of unstabilised polymers occurring during processing were found to be strongly dependent on the amount of oxygen present in the mixer. 2 ,6 ,3' ,5' -tetra-tert-butyl-4'-phenoxy-4-methylene-2, 5-cyclohexadiene-1- one (galvinoxyl), iodine, nitroxyl radicals and cupric stearate were found to be very efficient melt stabilisers particularly when processed in a restricted amount of air. The mechanisms of their melt stabilising action have been investigated and a common cyclical regenerative mechanism involving both chain-breaking electron acceptor (CB-A) and chain-breaking electron donor (CB-D) antioxidant activity was found to be involved in each case. 2,6,3',5'-tetra-tert-butyl-4'-hydroxy phenyl-4-rrethylene-2,5-cyclohexadiene- 1-one (hydrogalvinoxy1), 4-hydroxy, 2,2,6, 6-tetra methyl-N-hydroxy piperidine and hydrogen iodide were formed together with olefinic unsaturation in the substrates during the melt processing of the polymers containing galvinoxyl, 4-hydroxy, 2,2,6, 6-tetra methyl piperidine oxyl and iodine respectively. No bonding of the melt stabilisers to the polymers was found to occur. Cupric stearate was found to undergo a similar redox reaction during its action as a melt stabiliser with the formation of unsaturation in the polymer. Evidence for the above processes is presented. The behaviours of melt stabilisers in the subsequent thermal and photooxidation of polyolefins have also been studied. Galvinoxyl which is very effective under both mild and severe processing canditions has been found to be an effective antioxidant during thermal oxidation (oven ageing) and it is also moderately good. as a photo-stabiliser. Iodine and cupric stearate acted efficiently during melt stabilisation of polymers, however they were both ineffective as thermo-oxidative antioxidants and UV stabilisers. Although the melt stabilisation effectiveness of stable nitroxyl radicals (e.g. 4-hydroxy, 2,2,6,6-tetra methyl piperidineoxyl and Bis- (2,2,6 ,6-tetra methyl-4- piperidinyl-N-oxyl) sebacate) is not as high as that of galvinoxyl during processing particularly in excess of air, they have been found to be much more efficient as UV stabilisers for polyolefins. The reasons for this are discussed.

Stabilisation of metallocene ethylene-1-octene copolymers during multiple extrusions

The melt stabilising efficiency of antioxidants with different structures based on hindered phenols, phosphite esters, phosphonite and a lactone was examined during multi-pass extrusions at 265 °C in three metallocene ethylene-1-octene copolymers (m-LLDPE) having different extent of short chain branching (SCB) and one Zeigler copolymer (z-LLDPE) containing the same level of SCB corresponding to one of the m-LLDPE polymers. The effect of the different antioxidants, when used separately and in combination, was investigated by characterising the changes in the polymer's rheological behaviour, colour formation and structural changes based on unsaturated groups and carbonyl content during five multi-pass extrusions. The results showed that all stabilisation systems examined offered higher efficiency in the metallocene polymers compared to the Zeigler. The effect of the extent of SCB in the metallocene polymers on the stabilising efficacy of the antioxidant systems was also examined, and it was shown that it had a significant effect, with both single and combinations of antioxidants giving higher efficiency in the m-LLDPE polymer containing higher extent of SCB. The presence of the lactone HP136 in mixtures containing hindered phenol–phosphite antioxidant systems gave a higher melt stabilisation efficiency than in its absence and this has been attributed to a co-operative antioxidant reaction steps that take place between the antioxidants resulting in the possible regeneration of the lactone antioxidant through a redox reaction. In all the metallocene PE polymers examined, the biologically hindered phenol, Irganox E, was shown to be more effective than the conventionally hindered phenol Irganox 1076, when examined alone or in combination with phosphite esters.

Reaction-driven surface restructuring and selectivity control in allylic alcohol catalytic aerobic oxidation over Pd

Synchronous, time-resolved DRIFTS/MS/XAS cycling studies of the vapor-phase selective aerobic oxidation of crotyl alcohol over nanoparticulate Pd have revealed surface oxide as the desired catalytically active phase, with dynamic, reaction-induced Pd redox processes controlling selective versus combustion pathways.

HOCl-modified phosphatidylcholines induce apoptosis and redox imbalance in HUVEC-ST cells

Electrophilic attack of hypochlorous acid on unsaturated bonds of fatty acyl chains is known to result mostly in chlorinated products that show cytotoxicity to some cell lines and were found in biological systems exposed to HOCl. This study aimed to investigate more deeply the products and the mechanism underlying cytotoxicity of phospholipid-HOCl oxidation products, synthesized by the reaction of HOCl with 1-stearoyl-2-oleoyl-, 1-stearoyl-2-linoleoyl-, and 1-stearoyl-2-arachidonyl-phosphatidylcholine. Phospholipid chlorohydrins were found to be the most abundant among obtained products. HOCl-modified lipids were cytotoxic towards HUVEC-ST (endothelial cells), leading to a decrease of mitochondrial potential and an increase in the number of apoptotic cells. These effects were accompanied by an increase of the level of active caspase-3 and caspase-7, while the caspase-3/-7 inhibitor Ac-DEVD-CHO dramatically decreased the number of apoptotic cells. Phospholipid-HOCl oxidation products were shown to affect cell proliferation by a concentration-dependent cell cycle arrest in the G/G phase and activating redox sensitive p38 kinase. The redox imbalance observed in HUVEC-ST cells exposed to modified phosphatidylcholines was accompanied by an increase in ROS level, and a decrease in glutathione content and antioxidant capacity of cell extracts. © 2014 Elsevier Inc. All rights reserved.

Fundamental Pd0/PdII redox steps in cross-coupling reactions:homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings

C–C bond-forming, cross-coupling reactions of organohalides with nucleophilic compounds, catalysed by palladium, are amongst the most important chemical reactions available to the synthetic chemist. The intimate mechanisms of these reactions, involving Pd0/PdII redox steps, have been of great historical interest and continue to be so. The myriad of possible mechanisms is reviewed in this chapter. The interplay of mononuclear Pd species with higher order Pd species, e.g. nanoclusters/nanoparticles are considered as being equally important in cross-coupling reaction mechanisms. A focus is placed on trichotomic behaviour of cross-coupling catalytic manifolds, from homogeneous to hybrid homogeneous–heterogeneous to truly heterogeneous behaviour. For the latter, surface chemistry and metal atom leaching (and various experimental techniques) are broadly discussed. It is now clear that mechanism for general cross‐coupling reactions, that is as presented to undergraduate students studying Chemistry degrees across the world, is undoubtedly more complex than first thought. New opportunities for catalyst design have therefore emerged in the area of Pd nanoparticles and nanocatalysis, with some wonderful applications especially in chemical biology, providing a snapshot of what the future might hold.