Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates (AlPOs) by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids that are based on phosphates. Apart from phosphates, phosphites, arsenates, sulfates, sulfites, selenates, selenites etc. have also been investigated. In addition to the different anions, the framework compounds now encompass almost all the elements of the periodic table. The compounds exhibit wide variety and structural diversity. New building units, such as thiosulfate and borate have also been explored as a network builder in the formation of framework structures. In this thesis, the results of the investigations on open-framework metal thiosulfates, metal borates and metal sulfates are presented. The studies are aimed not only at the synthesis of the new compounds based on the new anions, but also their possible applications. In Chapter 1 of the thesis an overview of inorganic open-framework materials with different anions is presented. In Chapter 2 (Part A), the synthesis, structure and transformation of inorganic-organic hybrid open-framework cadmium thiosulfate are presented. The lack of stability of the thiosulfate ion in solution prompted the exploration of new approaches such as low temperature solvothermal methods, use of rigid linkers etc. The transformations of lower to higher dimensional structures have been accomplished. The possible mechanisms for such transformations were investigated. In Part B, the physical and chemical properties of the hybrid cadmium thiosulfate frameworks are presented. The studies indicate that the anionic dyes selectively adsorb on the compounds in the water medium and also desorb reasonably in alcoholic medium. The cadmium thiosulfate compounds appear to be reasonable photocalysts for the photodecomposition of the cationic dyes under UV irradiation as well as under sunlight with good recyclability. The compounds also exhibit heterogeneous catalytic behavior (Lewis acidity) for the cyanosilylation of the imines. In Chapter 3, a new family of organically templated open-framework borate materials is presented. The zinc and aluminoborate structures, prepared in the present study, are rationalized using the HSAB theory. The [B4O9H2] units polymerize differently to form different zinc borate structures. The amine molecules act as a ligand by binding with the metal. The nature of the amine appears to control the dimensionality of the final zinc borate structures. The zinc borate compounds exhibit absorption of UV-light (λ = 365 nm) suggesting that the zinc borate compounds could be exploited for UV-blocking applications. Organically templated aluminoborates have connectivities between the Al3+ ions and the [B5O10] cyclic pentaborate units. The aluminoborate structures exhibit graphite layer and three-dimensional diamond structure. Detailed studies and comparison of the various amine templated open-framework aluminoborate structures reveals subtle relationships between the organic amines (shape and length of the amines) and the final framework structures. In Chapter 3, the synthesis, structure and catalytic studies of a variety of cadmium sulfate phases have been carried out. Polyazaheterocyclic ligands were employed to study their possible role in the formation of such structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The connectivity between the Cd2+ and (SO4)2− ions form one-, two-and three-dimensionally extended cadmium sulfate phases, though the starting source is cadmium sulfate (CdSO4.8/3H2O) in all the cases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one-and two-dimensional structures. The interconnectivity between the two units gives rise to the final observed structure. As part of the study, a variety of properties i.e. adsorption-desorption, photocatalytic degradation and cyanosilylation reaction, exhibited by the cadmium sulfate compounds have been investigated and the properties are comparable to the cadmium thiosulfate phases. AlPOs are well known for their many important properties. The wide varieties in their structures and heterogeneous catalytic properties have been extensively investigated. The photocatalytic behaviors, on the contrary, have not been investigated in detail. The photocatalytic properties of the metal-doped AlPOs, for the photodegrdation of organic dyes have been investigated in the Chapter 5. The metal ions (Mg2+, Zn2+ and Co2+) have been substituted in place of Al3+ and Ti4+ in place of both the Al3+ and P5+ in a variety in AlPO structures and the synthesized phases are characterized by a variety of techniques. Photodecomposition studies of organic dye molecules under UV-light were carried out in aqueous medium. The studies suggest that the photocatalytic activity is reasonable and appears to depend on the dopant concentration. Ti-substituted phase exhibits the maximum catalytic activity.

Xylophagous borers and termites that damage "timber-in-service" cause millions of dollars loss annually throughout mainland Australia. I developed field-based feeding assays with practical relevance to preventative action and remedial treatment of infestations of xylophagous insects in the built environment. Essential to this work is facilitating a high termite risk by maintaining an environment conducive to sustained foraging by termites. Feeding assays conducted in low termite risk areas are unduly prolonged, with inherently erratic termite feeding responses. I successfully developed feeding assays with a high termite risk. To establish whether a physical barrier, retrofitted as a sleeve, could prevent termites from damaging wooden poles, eighty poles were established within Beerburrum State Forest, south-east Queensland, Australia. Poles within sets were interconnected with buried timber to facilitate a high risk to Coptotermes acinaciformis (Froggatt). Mesh sleeves to a depth of 1.5m did not prevent termite damage to the poles. Hoop pine Araucaria cunninghamii Ait. ex D.Don dowels ("dip-sticks") were useful termite monitoring devices on the poles. The depth of foraging by termites has implications for the effectiveness of retrofitted physical and chemical barriers in general. Timber quantity and quality has a pivotal influence on the aggregation of large numbers of feeding termites necessary for baiting work and for producing efficacy data of relevance to the protection of timber-in-service from termites. Seasonal variation in termite foraging was examined. Both C. acinaciformis and Coptotermes lacteus (Froggatt) were more active feeding in summer than in autumn. In general, mass loss followed mean ambient temperature. Suppression of C. acinaciformis feeding responses relative to C. lacteus during summer, particularly during January, is thought to be due to excessive temperatures in the containers attached to infested trees. Termite foraging behaviour and responses to both varying masses of softwood timbers and varying exposure times were investigated. The rate of mass loss was independent of the number of test specimens and appeared linear. Colonies regulate the number of foragers directly according to the mass of susceptible timber available. This phenomenon was exploited throughout the remainder of the thesis. Of particular significance was the considerable intra- and inter-specific variation in susceptibility of softwoods to C. acinaciformis and Mastotermes darwiniensis Froggatt. The sapwoods tested were susceptible, but the heartwoods were generally resistant to damage by termites. These data confirm that termites are discriminating feeders, and some more so than others. A novel methodology, developed to maintain an environment conducive to sustained foraging by termites during field-testing, is presented. Consistency in timber acceptance and susceptibility to termites is considered to be important in determining the frequency of inspection and the success of bait systems. I evaluate the termiticidal activity of the bait toxicants hexaflumuron and chlorfluazuron for the management of the subterranean termite C. acinaciformis in the field. The Sentricon Colony Elimination System with Baitube-devices containing 0.1% and 1% mass/mass (m/m) hexaflumuron bait toxicant in dry wood flour (Recruit) was successful in eliminating field colonies of C. acinaciformis. Similarly, the Exterra Termite Interception and Baiting System with cellulose-acetate powder containing either 0.05% m/m or 0.25% m/m chlorfluazuron (Requiem) eliminated C. acinaciformis. Indicators (including "dip-sticks") used to monitor colony health were reliable. By using C. acinaciformis, which builds mounds (epigeous nests) in northern Australia, I was able to avoid the use of multiple mark-release schemes to verify the effects of the bait toxicant on the termite colonies. Problems with multiple mark-release schemes, used elsewhere in the world, are discussed. I continued the focus on bait quality and placement by evaluating termite responses to two aspects of treated stakes, their attractiveness and their susceptibility. Three experiments were undertaken near Townsville and at Beerburrum, with Coptotermes and Schedorhinotermes. Whilst there were no significant differences in the rate of location and foraging, with respect to treatments, differences in foraging, with respect to C. acinaciformis and Schedorhinotermes seclusus (Hill) were significant. Coptotermes acinaciformis displayed greater foraging site tenacity than S. seclusus at Beerburrum. Increased consumption of bait, due to the addition of a phagostimulant, needs to be observed in the field before an increase in the efficacy of baits in a termite management program can be claimed. In Australia, softwood timbers are extensively used in building construction and are generally highly susceptible to damage by termites. I focussed on field feeding assays to test efficacy of borate-treated softwoods against termites and to define "adequate" protection thresholds. Laboratory and field data reported in the literature were confusing with regard to what constitutes "adequate" protection thresholds. The confusion was compounded by differences in termite species, timber species used and test methodology. Laboratory data indicated a borate loading of 0.5% m/m boric acid equivalent (BAE) would cause > 90% termite mortality and restrict mass loss in test specimens to 5%. Field data generally suggested that borate loadings in excess of 0.5% m/m BAE were required. The main contribution of the work to increasing our understanding of management options for termites in the built environment was in resolving the confusion between laboratory and field data for borate wood-preservatives. These apparently conflicting results were explained by the presence or absence of untreated feeder material in the test environment. In the absence of untreated feeder material, retention of 0.5% BAE provides adequate protection from Coptotermes sp., whereas in the presence of untreated feeder material, increased retentions are required. Furthermore, the retentions required increase with increased amounts of susceptible material. Some termites, Nasutitermes sp. and M. darwiniensis, for example, are borate-tolerant and borate wood-preservatives are not a viable management option. The lack of uniform standards for termite-test methodology and assessment criteria for efficacy across the world is recognized as a difficulty with research into the performance of wood preservatives with termites. The many variables in laboratory and field assays make "prescriptive" standards difficult to recommend. The use of "performance" standards to define efficacy criteria ("adequate" protection) is discussed. Whilst the majority of the work involves subterranean termites ("termites"), I examine the question of how to define a hardwood timber species as "not susceptible" to lyctine beetle damage. Aspects of the biology, behaviour and management of Lyctus brunneus (Stephens) are reviewed and a novel field sampling and testing protocol to establish lyctine susceptibility of timber species is presented. A sound understanding of the biology and behaviour of xylophagous insects in the field is essential to ensure that management options implemented in the built environment have a strong ecological basis. The success of this study in achieving stated aims, the need for further work and the implications for test methodologies in the field with practical relevance to infestations of xylophagous insects in the built environment are discussed.

Xylophagous borers and termites that damage "timber-in-service" cause millions of dollars loss annually throughout mainland Australia. I developed field-based feeding assays with practical relevance to preventative action and remedial treatment of infestations of xylophagous insects in the built environment. Essential to this work is facilitating a high termite risk by maintaining an environment conducive to sustained foraging by termites. Feeding assays conducted in low termite risk areas are unduly prolonged, with inherently erratic termite feeding responses. I successfully developed feeding assays with a high termite risk. To establish whether a physical barrier, retrofitted as a sleeve, could prevent termites from damaging wooden poles, eighty poles were established within Beerburrum State Forest, south-east Queensland, Australia. Poles within sets were interconnected with buried timber to facilitate a high risk to Coptotermes acinaciformis (Froggatt). Mesh sleeves to a depth of 1.5m did not prevent termite damage to the poles. Hoop pine Araucaria cunninghamii Ait. ex D.Don dowels ("dip-sticks") were useful termite monitoring devices on the poles. The depth of foraging by termites has implications for the effectiveness of retrofitted physical and chemical barriers in general. Timber quantity and quality has a pivotal influence on the aggregation of large numbers of feeding termites necessary for baiting work and for producing efficacy data of relevance to the protection of timber-in-service from termites. Seasonal variation in termite foraging was examined. Both C. acinaciformis and Coptotermes lacteus (Froggatt) were more active feeding in summer than in autumn. In general, mass loss followed mean ambient temperature. Suppression of C. acinaciformis feeding responses relative to C. lacteus during summer, particularly during January, is thought to be due to excessive temperatures in the containers attached to infested trees. Termite foraging behaviour and responses to both varying masses of softwood timbers and varying exposure times were investigated. The rate of mass loss was independent of the number of test specimens and appeared linear. Colonies regulate the number of foragers directly according to the mass of susceptible timber available. This phenomenon was exploited throughout the remainder of the thesis. Of particular significance was the considerable intra- and inter-specific variation in susceptibility of softwoods to C. acinaciformis and Mastotermes darwiniensis Froggatt. The sapwoods tested were susceptible, but the heartwoods were generally resistant to damage by termites. These data confirm that termites are discriminating feeders, and some more so than others. A novel methodology, developed to maintain an environment conducive to sustained foraging by termites during field-testing, is presented. Consistency in timber acceptance and susceptibility to termites is considered to be important in determining the frequency of inspection and the success of bait systems. I evaluate the termiticidal activity of the bait toxicants hexaflumuron and chlorfluazuron for the management of the subterranean termite C. acinaciformis in the field. The Sentricon Colony Elimination System with Baitube-devices containing 0.1% and 1% mass/mass (m/m) hexaflumuron bait toxicant in dry wood flour (Recruit) was successful in eliminating field colonies of C. acinaciformis. Similarly, the Exterra Termite Interception and Baiting System with cellulose-acetate powder containing either 0.05% m/m or 0.25% m/m chlorfluazuron (Requiem) eliminated C. acinaciformis. Indicators (including "dip-sticks") used to monitor colony health were reliable. By using C. acinaciformis, which builds mounds (epigeous nests) in northern Australia, I was able to avoid the use of multiple mark-release schemes to verify the effects of the bait toxicant on the termite colonies. Problems with multiple mark-release schemes, used elsewhere in the world, are discussed. I continued the focus on bait quality and placement by evaluating termite responses to two aspects of treated stakes, their attractiveness and their susceptibility. Three experiments were undertaken near Townsville and at Beerburrum, with Coptotermes and Schedorhinotermes. Whilst there were no significant differences in the rate of location and foraging, with respect to treatments, differences in foraging, with respect to C. acinaciformis and Schedorhinotermes seclusus (Hill) were significant. Coptotermes acinaciformis displayed greater foraging site tenacity than S. seclusus at Beerburrum. Increased consumption of bait, due to the addition of a phagostimulant, needs to be observed in the field before an increase in the efficacy of baits in a termite management program can be claimed. In Australia, softwood timbers are extensively used in building construction and are generally highly susceptible to damage by termites. I focussed on field feeding assays to test efficacy of borate-treated softwoods against termites and to define "adequate" protection thresholds. Laboratory and field data reported in the literature were confusing with regard to what constitutes "adequate" protection thresholds. The confusion was compounded by differences in termite species, timber species used and test methodology. Laboratory data indicated a borate loading of 0.5% m/m boric acid equivalent (BAE) would cause > 90% termite mortality and restrict mass loss in test specimens to 5%. Field data generally suggested that borate loadings in excess of 0.5% m/m BAE were required. The main contribution of the work to increasing our understanding of management options for termites in the built environment was in resolving the confusion between laboratory and field data for borate wood-preservatives. These apparently conflicting results were explained by the presence or absence of untreated feeder material in the test environment. In the absence of untreated feeder material, retention of 0.5% BAE provides adequate protection from Coptotermes sp., whereas in the presence of untreated feeder material, increased retentions are required. Furthermore, the retentions required increase with increased amounts of susceptible material. Some termites, Nasutitermes sp. and M. darwiniensis, for example, are borate-tolerant and borate wood-preservatives are not a viable management option. The lack of uniform standards for termite-test methodology and assessment criteria for efficacy across the world is recognized as a difficulty with research into the performance of wood preservatives with termites. The many variables in laboratory and field assays make "prescriptive" standards difficult to recommend. The use of "performance" standards to define efficacy criteria ("adequate" protection) is discussed. Whilst the majority of the work involves subterranean termites ("termites"), I examine the question of how to define a hardwood timber species as "not susceptible" to lyctine beetle damage. Aspects of the biology, behaviour and management of Lyctus brunneus (Stephens) are reviewed and a novel field sampling and testing protocol to establish lyctine susceptibility of timber species is presented. A sound understanding of the biology and behaviour of xylophagous insects in the field is essential to ensure that management options implemented in the built environment have a strong ecological basis. The success of this study in achieving stated aims, the need for further work and the implications for test methodologies in the field with practical relevance to infestations of xylophagous insects in the built environment are discussed.

Xylophagous borers and termites that damage "timber-in-service" cause millions of dollars loss annually throughout mainland Australia. I developed field-based feeding assays with practical relevance to preventative action and remedial treatment of infestations of xylophagous insects in the built environment. Essential to this work is facilitating a high termite risk by maintaining an environment conducive to sustained foraging by termites. Feeding assays conducted in low termite risk areas are unduly prolonged, with inherently erratic termite feeding responses. I successfully developed feeding assays with a high termite risk. To establish whether a physical barrier, retrofitted as a sleeve, could prevent termites from damaging wooden poles, eighty poles were established within Beerburrum State Forest, south-east Queensland, Australia. Poles within sets were interconnected with buried timber to facilitate a high risk to Coptotermes acinaciformis (Froggatt). Mesh sleeves to a depth of 1.5m did not prevent termite damage to the poles. Hoop pine Araucaria cunninghamii Ait. ex D.Don dowels ("dip-sticks") were useful termite monitoring devices on the poles. The depth of foraging by termites has implications for the effectiveness of retrofitted physical and chemical barriers in general. Timber quantity and quality has a pivotal influence on the aggregation of large numbers of feeding termites necessary for baiting work and for producing efficacy data of relevance to the protection of timber-in-service from termites. Seasonal variation in termite foraging was examined. Both C. acinaciformis and Coptotermes lacteus (Froggatt) were more active feeding in summer than in autumn. In general, mass loss followed mean ambient temperature. Suppression of C. acinaciformis feeding responses relative to C. lacteus during summer, particularly during January, is thought to be due to excessive temperatures in the containers attached to infested trees. Termite foraging behaviour and responses to both varying masses of softwood timbers and varying exposure times were investigated. The rate of mass loss was independent of the number of test specimens and appeared linear. Colonies regulate the number of foragers directly according to the mass of susceptible timber available. This phenomenon was exploited throughout the remainder of the thesis. Of particular significance was the considerable intra- and inter-specific variation in susceptibility of softwoods to C. acinaciformis and Mastotermes darwiniensis Froggatt. The sapwoods tested were susceptible, but the heartwoods were generally resistant to damage by termites. These data confirm that termites are discriminating feeders, and some more so than others. A novel methodology, developed to maintain an environment conducive to sustained foraging by termites during field-testing, is presented. Consistency in timber acceptance and susceptibility to termites is considered to be important in determining the frequency of inspection and the success of bait systems. I evaluate the termiticidal activity of the bait toxicants hexaflumuron and chlorfluazuron for the management of the subterranean termite C. acinaciformis in the field. The Sentricon Colony Elimination System with Baitube-devices containing 0.1% and 1% mass/mass (m/m) hexaflumuron bait toxicant in dry wood flour (Recruit) was successful in eliminating field colonies of C. acinaciformis. Similarly, the Exterra Termite Interception and Baiting System with cellulose-acetate powder containing either 0.05% m/m or 0.25% m/m chlorfluazuron (Requiem) eliminated C. acinaciformis. Indicators (including "dip-sticks") used to monitor colony health were reliable. By using C. acinaciformis, which builds mounds (epigeous nests) in northern Australia, I was able to avoid the use of multiple mark-release schemes to verify the effects of the bait toxicant on the termite colonies. Problems with multiple mark-release schemes, used elsewhere in the world, are discussed. I continued the focus on bait quality and placement by evaluating termite responses to two aspects of treated stakes, their attractiveness and their susceptibility. Three experiments were undertaken near Townsville and at Beerburrum, with Coptotermes and Schedorhinotermes. Whilst there were no significant differences in the rate of location and foraging, with respect to treatments, differences in foraging, with respect to C. acinaciformis and Schedorhinotermes seclusus (Hill) were significant. Coptotermes acinaciformis displayed greater foraging site tenacity than S. seclusus at Beerburrum. Increased consumption of bait, due to the addition of a phagostimulant, needs to be observed in the field before an increase in the efficacy of baits in a termite management program can be claimed. In Australia, softwood timbers are extensively used in building construction and are generally highly susceptible to damage by termites. I focussed on field feeding assays to test efficacy of borate-treated softwoods against termites and to define "adequate" protection thresholds. Laboratory and field data reported in the literature were confusing with regard to what constitutes "adequate" protection thresholds. The confusion was compounded by differences in termite species, timber species used and test methodology. Laboratory data indicated a borate loading of 0.5% m/m boric acid equivalent (BAE) would cause > 90% termite mortality and restrict mass loss in test specimens to 5%. Field data generally suggested that borate loadings in excess of 0.5% m/m BAE were required. The main contribution of the work to increasing our understanding of management options for termites in the built environment was in resolving the confusion between laboratory and field data for borate wood-preservatives. These apparently conflicting results were explained by the presence or absence of untreated feeder material in the test environment. In the absence of untreated feeder material, retention of 0.5% BAE provides adequate protection from Coptotermes sp., whereas in the presence of untreated feeder material, increased retentions are required. Furthermore, the retentions required increase with increased amounts of susceptible material. Some termites, Nasutitermes sp. and M. darwiniensis, for example, are borate-tolerant and borate wood-preservatives are not a viable management option. The lack of uniform standards for termite-test methodology and assessment criteria for efficacy across the world is recognized as a difficulty with research into the performance of wood preservatives with termites. The many variables in laboratory and field assays make "prescriptive" standards difficult to recommend. The use of "performance" standards to define efficacy criteria ("adequate" protection) is discussed. Whilst the majority of the work involves subterranean termites ("termites"), I examine the question of how to define a hardwood timber species as "not susceptible" to lyctine beetle damage. Aspects of the biology, behaviour and management of Lyctus brunneus (Stephens) are reviewed and a novel field sampling and testing protocol to establish lyctine susceptibility of timber species is presented. A sound understanding of the biology and behaviour of xylophagous insects in the field is essential to ensure that management options implemented in the built environment have a strong ecological basis. The success of this study in achieving stated aims, the need for further work and the implications for test methodologies in the field with practical relevance to infestations of xylophagous insects in the built environment are discussed.

Xylophagous borers and termites that damage "timber-in-service" cause millions of dollars loss annually throughout mainland Australia. I developed field-based feeding assays with practical relevance to preventative action and remedial treatment of infestations of xylophagous insects in the built environment. Essential to this work is facilitating a high termite risk by maintaining an environment conducive to sustained foraging by termites. Feeding assays conducted in low termite risk areas are unduly prolonged, with inherently erratic termite feeding responses. I successfully developed feeding assays with a high termite risk. To establish whether a physical barrier, retrofitted as a sleeve, could prevent termites from damaging wooden poles, eighty poles were established within Beerburrum State Forest, south-east Queensland, Australia. Poles within sets were interconnected with buried timber to facilitate a high risk to Coptotermes acinaciformis (Froggatt). Mesh sleeves to a depth of 1.5m did not prevent termite damage to the poles. Hoop pine Araucaria cunninghamii Ait. ex D.Don dowels ("dip-sticks") were useful termite monitoring devices on the poles. The depth of foraging by termites has implications for the effectiveness of retrofitted physical and chemical barriers in general. Timber quantity and quality has a pivotal influence on the aggregation of large numbers of feeding termites necessary for baiting work and for producing efficacy data of relevance to the protection of timber-in-service from termites. Seasonal variation in termite foraging was examined. Both C. acinaciformis and Coptotermes lacteus (Froggatt) were more active feeding in summer than in autumn. In general, mass loss followed mean ambient temperature. Suppression of C. acinaciformis feeding responses relative to C. lacteus during summer, particularly during January, is thought to be due to excessive temperatures in the containers attached to infested trees. Termite foraging behaviour and responses to both varying masses of softwood timbers and varying exposure times were investigated. The rate of mass loss was independent of the number of test specimens and appeared linear. Colonies regulate the number of foragers directly according to the mass of susceptible timber available. This phenomenon was exploited throughout the remainder of the thesis. Of particular significance was the considerable intra- and inter-specific variation in susceptibility of softwoods to C. acinaciformis and Mastotermes darwiniensis Froggatt. The sapwoods tested were susceptible, but the heartwoods were generally resistant to damage by termites. These data confirm that termites are discriminating feeders, and some more so than others. A novel methodology, developed to maintain an environment conducive to sustained foraging by termites during field-testing, is presented. Consistency in timber acceptance and susceptibility to termites is considered to be important in determining the frequency of inspection and the success of bait systems. I evaluate the termiticidal activity of the bait toxicants hexaflumuron and chlorfluazuron for the management of the subterranean termite C. acinaciformis in the field. The Sentricon Colony Elimination System with Baitube-devices containing 0.1% and 1% mass/mass (m/m) hexaflumuron bait toxicant in dry wood flour (Recruit) was successful in eliminating field colonies of C. acinaciformis. Similarly, the Exterra Termite Interception and Baiting System with cellulose-acetate powder containing either 0.05% m/m or 0.25% m/m chlorfluazuron (Requiem) eliminated C. acinaciformis. Indicators (including "dip-sticks") used to monitor colony health were reliable. By using C. acinaciformis, which builds mounds (epigeous nests) in northern Australia, I was able to avoid the use of multiple mark-release schemes to verify the effects of the bait toxicant on the termite colonies. Problems with multiple mark-release schemes, used elsewhere in the world, are discussed. I continued the focus on bait quality and placement by evaluating termite responses to two aspects of treated stakes, their attractiveness and their susceptibility. Three experiments were undertaken near Townsville and at Beerburrum, with Coptotermes and Schedorhinotermes. Whilst there were no significant differences in the rate of location and foraging, with respect to treatments, differences in foraging, with respect to C. acinaciformis and Schedorhinotermes seclusus (Hill) were significant. Coptotermes acinaciformis displayed greater foraging site tenacity than S. seclusus at Beerburrum. Increased consumption of bait, due to the addition of a phagostimulant, needs to be observed in the field before an increase in the efficacy of baits in a termite management program can be claimed. In Australia, softwood timbers are extensively used in building construction and are generally highly susceptible to damage by termites. I focussed on field feeding assays to test efficacy of borate-treated softwoods against termites and to define "adequate" protection thresholds. Laboratory and field data reported in the literature were confusing with regard to what constitutes "adequate" protection thresholds. The confusion was compounded by differences in termite species, timber species used and test methodology. Laboratory data indicated a borate loading of 0.5% m/m boric acid equivalent (BAE) would cause > 90% termite mortality and restrict mass loss in test specimens to 5%. Field data generally suggested that borate loadings in excess of 0.5% m/m BAE were required. The main contribution of the work to increasing our understanding of management options for termites in the built environment was in resolving the confusion between laboratory and field data for borate wood-preservatives. These apparently conflicting results were explained by the presence or absence of untreated feeder material in the test environment. In the absence of untreated feeder material, retention of 0.5% BAE provides adequate protection from Coptotermes sp., whereas in the presence of untreated feeder material, increased retentions are required. Furthermore, the retentions required increase with increased amounts of susceptible material. Some termites, Nasutitermes sp. and M. darwiniensis, for example, are borate-tolerant and borate wood-preservatives are not a viable management option. The lack of uniform standards for termite-test methodology and assessment criteria for efficacy across the world is recognized as a difficulty with research into the performance of wood preservatives with termites. The many variables in laboratory and field assays make "prescriptive" standards difficult to recommend. The use of "performance" standards to define efficacy criteria ("adequate" protection) is discussed. Whilst the majority of the work involves subterranean termites ("termites"), I examine the question of how to define a hardwood timber species as "not susceptible" to lyctine beetle damage. Aspects of the biology, behaviour and management of Lyctus brunneus (Stephens) are reviewed and a novel field sampling and testing protocol to establish lyctine susceptibility of timber species is presented. A sound understanding of the biology and behaviour of xylophagous insects in the field is essential to ensure that management options implemented in the built environment have a strong ecological basis. The success of this study in achieving stated aims, the need for further work and the implications for test methodologies in the field with practical relevance to infestations of xylophagous insects in the built environment are discussed.

Στην παρούσα διατριβή ερευνήθηκε η αξιοποίηση μεταλλευτικών, βιομηχανικών παραπροϊόντων, των στερεών Υπολειμμάτων Βορίου (ΥΒ), που δημιουργούνται σε διάφορα στάδια κατά την παραγωγική διαδικασία προϊόντων βορίου. Τα εν λόγω παραπροϊόντα, που κατηγοριοποιούνται σε πέντε ποιότητες, SBW, DBW, SSBW, TBW και MBW, χρησιμοποιήθηκαν ως πρόσθετο Α’ υλών για την παραγωγή τούβλων και κεραμιδιών, και ως Α΄ ύλη για την παρασκευή τεχνητών ελαφροαδρανών. Πραγματοποιήθηκε φυσικοχημικός χαρακτηρισμός και θερμική ανάλυση όλων των ΥΒ. Στη συνέχεια μελετήθηκε η επίδραση προσθήκης διαφορετικών συγκεντρώσεων ΥΒ (SBW και SSBW) σε αργιλούχες Α΄ ύλες. Έγινε μια πρώτη προσέγγιση παρασκευής και ελέγχου κεραμικών δοκιμίων με τη μέθοδο της ξηρής ανάμιξης και αξονικής συμπίεσης, προκειμένου να περιοριστεί το φαινόμενο διάχυσης υδατοδιαλυτών ενώσεων βορίου που περιέχονται στα ΥΒ. Η προσθήκη 5%κβ SSBW και θερμοκρασία όπτησης 900-950°C οδήγησε σε κεραμικά με παραπλήσιες ή ακόμα και βελτιωμένες ιδιότητες (αυξημένες μηχανικές αντοχές) συγκριτικά με τα κεραμικά αναφοράς. Επιπλέον εξετάστηκε η παραγωγή δειγμάτων με ΥΒ (SBW) και διάλυμα εμπορίου με βορικό (Evansite®) ακολουθώντας διαδικασία παραπλήσια της βιομηχανικής πρακτικής. Στους 1000°C, παρατηρήθηκε μείωση της απορρόφησης νερού και αύξηση της αντοχής σε κάμψη για τα δείγματα με βορικά, σε σύγκριση με τα δείγματα αναφοράς. Η προσθήκη βορικών ευνόησε τη δημιουργία νέων κρυσταλλικών κατά την όπτηση. Δεδομένης της χημικής και ορυκτολογικής σύνθεσης των ΥΒ (πλούσια σε συλλιπάσματα και υψηλές απώλειες πύρωσης), πραγματοποιήθηκε επιπρόσθετα μελέτη των φυσικοχημικών μηχανισμών θερμικής διάσπασής τους. Σε θερμαινόμενη τράπεζα παρατηρήθηκε η ικανότητα διόγκωσης και ανάπτυξης ρευστής φάσης των ΥΒ, καθώς και μιγμάτων αυτών με άλλα υλικά, με σκοπό την εργαστηριακή παραγωγή ελαφροαδρανών. Βάσει των αποτελεσμάτων προτάθηκε ένα μίγμα αποτελούμενο από 70%κβ ΥΒ, 20%κβ αργιλούχο μίγμα και 10%κβ χαλαζιακή άμμο, για τη μορφοποίηση ξηρών σφαιριδίων. Απότομη θέρμανσή τους στους 760°C οδήγησε σε πορώδη υαλοποιημένα αδρανή με φαινόμενη πυκνότητα <1g/cm3. Το ενεργειακό κόστος παραγωγής των συγκεκριμένων αδρανών είναι χαμηλότερο, καθώς παρατηρήθηκε μείωση στη θερμοκρασία σε σχέση με άλλα τεχνητά ελαφροαδρανή, που παρασκευάζονται στους 1100°C. Για την αντιμετώπιση της διάχυσης ενώσεων βορίου προς την επιφάνεια των ξηρών σφαιριδίων, που οδήγησε σε προβλήματα κατά την πειραματική διαδικασία και σε υποβάθμιση της ποιότητας των τελικών προϊόντων, εξετάστηκε η προσθήκη φρουκτόζης ως παρεμποδιστή στο μίγμα Α’ υλών, με στόχο την βελτιστοποίηση της διαδικασίας παραγωγής ελαφροαδρανών από ΥΒ. Προσθήκη έστω και 0.5%κβ φρουκτόζης οδήγησε σε ικανοποιητικό έλεγχο, ενώ οι φυσικές ιδιότητες των παραχθέντων αδρανών τα κατατάσσουν στην κατηγορία των ελαφροαδρανών, σύμφωνα με το πρότυπο ASTM 330-97. Τα αποτελέσματα οδήγησαν στην κατανόηση βασικών φαινομένων θερμικής διάσπασης και στην ανάπτυξη μιας βέλτιστης διεργασίας παραγωγής τεχνητών ελαφροαδρανών χρησιμοποιώντας ΥΒ ως εναλλακτικές Α’ ύλες, με προφανές ενεργειακό και περιβαλλοντικό όφελος. / In the present thesis, the valorisation of mining and industrial by-products, the solid boron-containing Wastes (ΒW), which are created at various stages during the production process of concentrated and refined boron products, were investigated. The by-products under consideration, existing in five types SBW, DBW, SSBW, TBW and MBW, were used as additives and raw materials in clay mixes for the production of heavy clay ceramics (bricks, tiles and artificial lightweight aggregates). The BW were characterised in means of chemical and mineralogical composition and studied for their thermal behaviour. In addition, clay mixes with different amounts of BW (SBW and SSBW) were studied. A first approach was made on the formation of ceramic samples by dry pressing in order to minimize the borate migration towards the surface. The physical and mechanical properties, as well as the microstructure of the final products were studied. For 5 wt% SSBW addition and firing at 900-950°C, the sintered bodies presented comparable or improved physical and mechanical properties with respect to the reference formulation. Moreover, SBW or a commercial available borate solution (Evansite®) were introduced in a clay-based mix aiming to investigate their behaviour during a processing cycle comparable with that followed in the heavy clay industry. For firing at 1000°C, water absorption was reduced and bending strength increased for the samples with borates, compared to the reference samples. The addition of borates resulted in the formation of new crystalline phases during firing at high temperatures. BW consist of important fluxing oxides as well as of gas producing minerals during firing. Tests were performed on the bloating behavior of BW and mixes of them with other materials, by means of heating microscopy, aiming at the laboratorial production of lightweight aggregates (LWA). A new mix was proposed, according to the obtained results, consisting of 70wt% BW, 20wt% clay mixture and 10wt% quartz sand, for the formation of pellets. Abrupt heating of the dry pellets at 760°C, for 5min, resulted in porous LWA with bulk density <1g/cm3. The process was less energy demanding as the temperature was reduced compared to the one of the synthetic aggregates produced, where the firing temperature is 1100°C. During drying a white layer of boron salts was formed on the surface of the green pellets, which result on firing of a glassy layer causing alterations of their surface and experimental difficulties. In order to address this problem, fructose was added in the raw mix as a migration inhibitor. Addition of even 0.5wt% fructose inhibited the salt formation and a glassy impervious layer was formed after firing. The physical properties of the final samples meet the requirements of LWA according to the standard ASTM 330-97. The results of this thesis, led to the development of an optimised process for the production of artificial LWA with BW, as an alternative raw material.

In order to improve the purity of steel castings, the use of special reactive coatings on carbon-bonded ceramic foam filters was explored. Carbon nanotubes were dispersed in water by means of ultrasonic treatment, using xanthan gum to stabilize the nanotubes in suspension and control the rheological behavior. The coatings were applied by cold spraying and binding was achieved during heat treatment in reducing atmosphere, thanks to an artificial pitch added to the slurry. The coated filters were successfully immersed in molten steel for different times. The thickness of the first alumina layer generated at the interface was independent of the immersion time: concentration gradients through its thickness suggested that the formation of this structure is limited by diffusion. Investigation of the steel after solidification by means of ASPEX showed that the presence of the coating influenced the size as well as the chemical composition of the remaining inclusions. Nano-coated filters had the best filtration efficiency (up to 95% for alumina inclusions after 10 s), but longer tests resulted in worse performance. In addition, coatings based on calcium aluminates in combination with carbon showed an efficiency greater than 97% for steel samples taken directly from the melt.

In order to improve the purity of steel castings, the use of special reactive coatings on carbon-bonded ceramic foam filters was explored. Carbon nanotubes were dispersed in water by means of ultrasonic treatment, using xanthan gum to stabilize the nanotubes in suspension and control the rheological behavior. The coatings were applied by cold spraying and binding was achieved during heat treatment in reducing atmosphere, thanks to an artificial pitch added to the slurry. The coated filters were successfully immersed in molten steel for different times. The thickness of the first alumina layer generated at the interface was independent of the immersion time: concentration gradients through its thickness suggested that the formation of this structure is limited by diffusion. Investigation of the steel after solidification by means of ASPEX showed that the presence of the coating influenced the size as well as the chemical composition of the remaining inclusions. Nano-coated filters had the best filtration efficiency (up to 95% for alumina inclusions after 10 s), but longer tests resulted in worse performance. In addition, coatings based on calcium aluminates in combination with carbon showed an efficiency greater than 97% for steel samples taken directly from the melt.

No description available.

The aim of this thesis was to introduce and apply the possibilities of using waste glycerol from biodiesel production and partly waste low-stiffen coolant from cars that could be applied in industry. At the beginning of the thesis is summarized biodiesel production and its world production. There is more developed biodiesel production in the Czech Republic and in the European Union and some European legal regulations and standards for biodiesel. Also described herein is a composition of biodiesel and the description of the technology of its production. In the theoretical section summarizes the physical and chemical properties of glycerol and there is also summarized the traditional use of glycerol as food, explosives, etc. There are also new procedures that were performed in the experimental part of the thesis. There are described the ion exchange mechanism, ion exchange resin properties and the properties of the acids and salts generated by neutralization with NaOH contained in the waste glycerol. Also is described herein the wood protection and properties of ethylene glycol coolants and properties of boroglycerol and boroglycol as protection for wood and mechanism of their preparation. Next is described the mechanism of dehydration of glycerol to acrolein and options which can perform the synthesis. In the experimental part, the pH of waste glycerol was measured, then was measured the exact amount of NaOH in the glycerol. There is also desribed cleaning of waste glycerol from NaOH using acidic cation exchange resins on columns, or by neutralization with oleic acid, lactic acid and CO2. Further syntheses were performed glycerol borate and ethylene glycol borate. Water amount in ethylene glycol and methanol with water amount in glycerol were found by distillation. Then were prepared boroglycol and boroglycerol. By the amount resulting from the amount of reaction water were observed reaction conditions H3BO3, Na2B4O7•10 H2O and glycerol. At the end was carried out experimental dilution resulting boroglycerol and boroglycol by ethanol, methanol, TMB. Finally, the diluted boroglycerol was deposited on wood. Dehydration of glycerol to acrolein under the catalytic action of KHSO4 was performed. The results are given all the results and discussed the possibility of using the knowledge gained in this work in the industry. In conclusion, there are listed the economic comparison using waste glycerol and crude oil as a raw material and also charts the development of oil prices in 40 years since 1970, and graph of the price of waste glycerol.