Analysis of rubber vulcanisates

A study has been made, using High Pressure Liquid Chromatography, of the migration of TMQ (a quinoline type) and 6PPD (a paraphenylenediamine type) antidegradants from a tyre sidewall compound into adjacent casing and liner compounds containing no antidegradant. Migration takes place at a rapid rate, even during the vulcanisation of the composite. After 4000 hours ageing in nitrogen at 100oC, there is a higher level of antidegradants in the casing than in the sidewall. An equilibrium distribution is not obtained. After 114 days at 50oC in 95% relative humidity, the level of solvent extractable 6PPD fell to zero, but subsequent ageing for 2 years in 50 pphm ozone showed no evidence of sidewall cracking. It is suggested that the antidegradant is still active but linked to the polymer chain. An analytical method, for the type and amount of sulphenamide accelerators in vulcanised rubber compounds, has been developed. During the vulcanisation process, the accelerators decay, liberating specific amines which have been solvent extracted, derivatised with 1-chloro-2,4-dinitrobenzene and the yellow coloured zwitter ion analysed using High Pressure Liquid Chromatography. The decay of the accelerator and sulphur during the vulcanisation process, has been studied. It has been demonstrated that the sulphur crosslinking with a styrenebutadiene polymer is a first order reaction, after an initial period during which the accelerator content falls to zero. Variations in sulphur to accelerator ratios gave consistent rate constants for the crosslinking, except for a sulphur level of less than 1% by weight and a ratiio of accelerator to sulphur of 1:1.3. The retention time of the reaction product between sulphur and accelerator from an HPLC column changes with cure time, showing that the precurser to crosslinking is an ever changing material. One of these reaction products has been analysed.

Knowledge acquisition from L2 specialist texts

This research aims to investigate knowledge acquisition and concept formation in the domain of economics and business studies through a foreign language, English, from the very initial to the very final stage of development in the context of Higher Education in Turkey. It traces both the processes as well as the product of acquisition in order to provide a detailed picture of how knowledge acquisition occurs. It aims to explore ways in which the acquisition process can be facilitated and promoted while prospective students of the Department of Economics and Business Administration receive a language training programme, following the completion of which they will join their academic community which offers part of its courses through the English language. The study draws upon (some) theories of mental representation of knowledge, such as schema, frame and script. The concept of discourse community with its characteristics is investigated, enculturation of prospective students to acquire knowledge of their domain through L2 is explored, and the crucial role of the constructivist theory in relation to knowledge acquisition is highlighted. The present study was conducted through a process of enculturation taking place partly at the language centre of Çukurova University and partly at the target discourse community. The data utilised for initiating knowledge acquisition was obtained by establishing a corpus of economics and business texts, which the learners are expected to read during their academic courses utilising computerised technology. The method of think aloud protocols was used to analyse processes taking place in knowledge acquisition, while the product of what was acquired was investigated by means of written recall protocols. It has been discovered that knowledge acquisition operates on the basis of analogical and to a certain extent metaphorical reasoning. The evidence obtained from the think aloud protocols showed that neophytes were able to acquire fundamental concepts of their future domain by reaching the level of shared understanding with the members of their target community of the faculty. Diaries and questionnaire analyses demonstrated that enculturation facilitated learners' transition from the language centre into the target community. Analyses of the written recall protocols and examinations from the post-enculturation stage of the research showed that neophytes' academic performances in their target community were much higher than those of their non-enculturated counterparts. Processes learners go through and strategies they spontaneously make use of, especially while acquiring knowledge of a specific domain through L2 have so far remained unexplored research areas. The present research makes a potential contribution to the language and knowledge acquisition theories by examining closely and systematically the language and the strategies they employ in acquiring such knowledge. The research findings offer useful implications to English language teaching at language schools. Language teachers are provided with useful guidelines as to how they can provide prospective students of a particular academic community with an experience of acquiring fundamental concepts of their discipline before they become members of their target community.

From postgraduate student to published writer:discourse variation and development in TESOL

This thesis is part of a project whose overall aim is to assist participants on an MSc TESOL course who wish to begin to publish articles in the field to do so. The project, which is undertaken within a naturalistic paradigm, has two intimately related and mutually constitutive strands: one descriptive, one interventionist. The descriptive strand consists of an analytical model of the TESOL article genre, and it is instantiated in this thesis. The interventionist strand consists of a series of pedagogic interactions and materials intended to assist project participants formulate a text suitable for publication within the target genre, and it is reported on in this thesis. I begin the thesis by looking in detail at the research approach which characterises the project. I then attempt to explain the situational context of the work and to position it within the context of other research in the areas of discourse community membership, academic genres, genre learning and academic enculturation. Having thus contextualised the work, I next attempt a detailed exploration of the problems of postgraduate students in TESOL when first attempting to write in the TESOL article genre: this exploration is undertaken from both a linguistic and a pedagogic perspective. Then in subsequent chapters, both a linguistic and a pedagogic response to these problems are proposed: the first consisting of an analytical model of the target genre, the second consisting of a series of pedagogic interactions and materials. The relationships between the two lines of response are also examined in some detail. Then in the final part of the thesis, I report feedback from the interventionist strand and attempt to conduct an evaluation of the whole project to date. Criteria for evaluation are proposed and examined in some detail in the context of the research approach of the project. The concluding chapter is a brief discussion of future directions for this work.

Sulfate-enhanced catalytic destruction of 1,1,1-trichlorethane over Pt(111)

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C−C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO−SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

Propene combustion over a model Pt/Al2O3/NiAl{110} catalyst

The genesis of a catalytically active model Pt/Al2O3/NiAl{110} oxidation catalyst is described. An ultrathin, crystalline γ-Al2O3 film was prepared via direct oxidation of a NiAl{110} single-crystal substrate. The room-temperature deposition of Pt clusters over the γ-Al2O3 film was characterised by LEED, AES and CO titration and follows a Stranski–Krastanov growth mode. Surface sulfation was attempted via SO2/O2 adsorption and thermal processing over bare and Pt promoted Al2O3/NiAl{110}. Platinum greatly enhances the saturation SOx coverage over that of bare alumina. Over clean Pt/γ-Al2O3 surfaces some adsorbed propene desorbs molecularly [similar]250 K while the remainder decomposes liberating hydrogen. Coadsorbed oxygen or sulfate promote propene combustion, with adsorbed sulfoxy species the most efficient oxidant. The chemistry of these alumina-supported Pt clusters shows a general evolution from small polycrystalline clusters to larger clusters with properties akin to low-index, Pt single-crystal surfaces.

A fast XPS study of sulphate promoted propene decomposition over Pt{111}

SO2 oxidation has been followed by Fast XPS over Pt{111}. Preadsorbed oxygen reduces the low temperature saturation coverage of SO2 with respect to the clean surface. Heating a mixed O2/SO2 adlayer results in efficient oxidation of both upright and flat-lying SO2 molecules to surface-bound SO4. Sulphate decomposes above room temperature liberating gas-phase SO2 and SO3. Propene adsorbs molecularly at 100 K over clean Pt{111} and dehydrogenates above 250 K to form a stable propylidyne adlayer, which in turn decomposes above 400 K to form graphitic carbon. Preadsorbed surface sulphate enhances the sticking probability of propene via formation of an alkyl-sulphate complex. Thermal decomposition of this complex accounts for low temperature propene combustion and is accompanied by atomic sulpur deposition. Propylidyne forms as on clean Pt but is less reactive undergoing partial oxidation above 450 K with residual surface oxygen.

Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction?

Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

Tail gas catalyzed N2O decomposition over Fe-beta zeolite. On the promoting role of framework connected AlO6 sites in the vicinity of Fe by controlled dealumination during exchange

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.