Some aspects of the microbiological properties of polymers and composite materials

The interaction of microorganisms with glass-reinforced polyester resins(GRP), both under laboratory and simulated operating conditions, has been examined following reports of severl! fungal biodeterioration. Although GRP was not previously associated with substantial microbial growth, small amounts of microbial activity would pose problems for products associated with comestible materials. The microbiology of the raw materials was investigated, two ingredients were supportive to microbial populations whilst five materials were biostatic or inhibitory in their action. Production laminate was not susceptible to microbial deterioration or inhibitory to microbes. Incorporation of zinc stearate, one of the supportive ingredients, at 300% manufacturing level or drastic undercuring produced laminate capable of supporting microbial growth but only after a non-biotic stage of degradation. Study of the long-term population dynamics of cisterns of GRP and competitive materials under conditions simulating in-service conditions, monitoring microbial numbers within the experimental vessels and comparing with the populations of the supply water, suggests that the performance of GRP cisterns is slightly superior to conventional competitive materials. An investigation of the biological performance of GRP cisterns in an isolated area of known microbiological hazard was conducted. Severe biodeterioration had been experienced with Preform GRP articles moulded using different production techniques, but substitution of current GRP articles resulted in no recurrence of the problem. All attempts to establish the fungal isolate responsible for the phenomena in cisterns under controlled conditions failed. Scanning Electron Microscopy of GRP surfaces showed that although differences exist between current and Preform laminates, these could not satisfactorily explain the differences in service behaviour. These results and the results of the British Plastics Federation Expert Working Group interlaboratory study are discussed in relation to the original report of gross fungal biodeterioration and, to the design of future testing programmes for the products of industrial concerns.

Characterisation of a cavity transfer mixer as a chemical reactor

This research project examined the feasibility of using a cavity transfer mixer (CTM) as a continuous reactor to perform reactions between either solid or liquid reagents and polymer melt; reactions which have previously been typically carried out in batch reactor systems. Equipment has been developed to allow uniform and reproducible introduction of reagents into the polymer melt. Reactions have also been performed using batch processing equipment to enable comparison with the performance of the CTM. It was concluded that: a) there are certain reactions which cannot be carried out in a CTM, but which can be performed in a batch system such as a mill or a sigma blade mixer. This was found to be the case for some neutralisation reactions where the product was quasi crosslinked. b) the reactions that can be carried out in a CTM are performed more efficiently in a CTM than on a batch process. For example, when monomers were to be grafted onto polymers, this was more safely and efficiently performed in the CTM than in a mill or a sigma blade mixer. Residence time distributions (RTDs) for three CTMs were studied in order to gain an insight into the effect of CTM geometry on RTD, polymer melt flow pattern and reactor performance. A mathematical model has been developed to predict the influence of process parameters on RTD and the results compared with experimentally observed trends. The comparison was good. A programme of research has been drawn up to form the basis of an industrially based sponsored development project of the CTM reactor. This work programme was successfully marketed to companies with commercial interest in modified rubber and plastics as an integral part of the research programme of this thesis and the sponsored research programme has paralleled the work reported here.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.

Thermal decomposition behavior of 1,2-bis-(2,4,6-tribromophenoxy)ethane

The thermal decomposition behavior of 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE) widely used as flame retardant plastics additive was studied by HRTG and differential scanning calorimetries. It was pyrolysed in inert atmosphere at 240 and 340 °C in isothermal conditions, the decomposition products were collected and investigated by means of IR and GC-MS, most of them are identified. It was found that BTBPE mostly evaporates at 240 °C. The decomposition products at 340°C depend on rate of their removal from the hot reaction zone. Main primary decomposition products found in case of rapid removal are tribromophenol and vinyl tribromophenyl ether. Whereas, prolonged contact with heating zone also produces hydrogen bromide, ethylene bromide, polybrominated vinyl phenyl ethers and diphenyl ethers, and dibenzodioxins. The nature of the identified compounds are in accordance with a molecular and radical pyrolysis reaction pathway. © 2002 Elsevier Science B.V. All rights reserved.

Waste 4:electronic-scrap recycling

The Haloclean process, a rotary kiln process for pyrolysis, developed by researchers at the Forschungszentrum Karlsruhe, Germany makes it possible to recover copper and precious metals from the scrap, ready for recycling. Pyrolysis neatly turns brominated electronic scrap plastics into recyclable copper and methanol feedstock while removing the halogens. The process has demonstrated its ability to recycle brominated electronic scrap in extensive parametric studies. A method suitable for the selective production of HBr in the presence of chlorine is the treatment of the pyrolysis oils with molten polypropylene. This treatment is offers the possibility to use the gas and liquid fraction from pyrolysis of electronic scrap as fossil fuel substitute in copper smelter processes or as feedstock for methanol production via gasification.

Composites take off without a parachute

The review is devoted to the cost effectiveness of composite materials applications as compared with their high performance characteristics. The use of reinforced plastics, ceramic matrix and metal matrix composites reinforced by carbon and graphite fibers in aerospace industry is considered. Until recently, the two major drivers for the application of composites in engines have been weight reduction and performance improvement. As shown, today a major challenge to be met by the industry is cost reduction.

Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Az SAP-rendszer fejlesztése egy műanyag-feldolgozó vállalatnál (Development of SAP system in a plastic manufacturing company)

Az SAP-rendszernek a kontrollingszervezetek működésére gyakorolt pozitív hatása nem titok. A visszacsatolás lehetőségének biztosításával alkalom nyílik a szervezetek tevékenységének követésére, ellenőrzésére, felülbírálására. A logisztika mint az egész vállalatot átszövő rendszer, működésének nyomon követése is létfontosságúvá vált, hiszen összetettségéből kifolyólag jellegzetességei, színvonala az egész rendszerre hatást gyakorol. A logisztikai rendszer és folyamatainak figyelemmel kísérésére a logisztikai kontrollingrendszer nyújt megoldást, visszacsatolási pontjain keresztül. A műanyag-feldolgozó vállalat esetében a szervezeti SAP-rendszer logisztikai kontrollingterületének fejlesztésétől várják a szervezeti hatékonyság emelkedését és a jobb színvonal elérését. _____ Positive effect of the SAP system on the operation of controlling organisations has not been a secret. Opportunity of the feedback will be possible to track, control, override operation of the organisations. The logistic controlling system provides a solution through feedback points for monitoring the logistic system and processes. In the case of plastics manufacturing company the increasing of organisational efficiency and achievement of a better standard is anticipated from development of logistic controlling area of the organisational SAP system.

Optimizing the Synthesis of AZN

Azulenyl nitrone (AZN) is a bright green compound that can be used to stain different compounds, including plastics. When these stained plastics are irradiated, as they commonly are in the sterilization of medical devices, AZN changes color from green to red, constituting a permanent change. This would make obsolete the current methods of radioactive labeling and maintain the integrity of medical equipment. Although a method of synthesis is already in place, the aim was to improve the yield significantly and find a more efficient and cost-effective procedure. Last year, the procedure used resulted in 18 to 20% of AZN synthesized at the most favorable conditions. With that in mind, this year modifications were done in the hopes of improving the yield. The solvent was changed to a mixture of isopropanol and triethylamine, a stronger base, and a catalytic amount of N-tertbutyl hydroxylamine hydrochloride was used (around 4 equivalents). The reaction time was also increased to 7 days, rather than 2. After several trials, the samples were run through column chromatography and the average yield was 70%, a much more promising result than that obtained last year. There is still research to be done to improve the technicalities of the procedure, including altering the amounts of N-tertbutyl hydroxylamine hydrochloride to try and obtain similar data with fewer amounts. This portion of the research will be done in the second half of the year. In the meantime, however, a novel and more efficient method of synthesis has been established for the production of AZN that can be potentially commercialized.

Optimizing the Synthesis of AZN

Azulenyl nitrone (AZN) is a bright green compound that can be used to stain different compounds, including plastics. When these stained plastics are irradiated, as they commonly are in the sterilization of medical devices, AZN changes color from green to red, constituting a permanent change. This would make obsolete the current methods of radioactive labeling and maintain the integrity of medical equipment. Although a method of synthesis is already in place, the aim was to improve the yield significantly and find a more efficient and cost-effective procedure. Last year, the procedure used resulted in 18 to 20% of AZN synthesized at the most favorable conditions. With that in mind, this year modifications were done in the hopes of improving the yield. The solvent was changed to a mixture of isopropanol and triethylamine, a stronger base, and a catalytic amount of N-tertbutyl hydroxylamine hydrochloride was used (around 4 equivalents). The reaction time was also increased to 7 days, rather than 2. After several trials, the samples were run through column chromatography and the average yield was 70%, a much more promising result than that obtained last year. There is still research to be done to improve the technicalities of the procedure, including altering the amounts of N-tertbutyl hydroxylamine hydrochloride to try and obtain similar data with fewer amounts. This portion of the research will be done in the second half of the year. In the meantime, however, a novel and more efficient method of synthesis has been established for the production of AZN that can be potentially commercialized.