Refine
Year of publication
- 2019 (31) (remove)
Document Type
- Doctoral Thesis (31) (remove)
Keywords
- Inklusion (2)
- Parteienkommunikation (2)
- Weinbau (2)
- Aluminiumorthophosphat (1)
- Aufsatzdidaktik (1)
- Behinderungen (1)
- Bologna-Prozess (1)
- Bororthophosphat (1)
- Calcium (1)
- Chancengerechtigkeit (1)
Institute
- Fachbereich 7 (5)
- Fachbereich 8 (3)
- Institut für Integrierte Naturwissenschaften, Abt. Biologie (2)
- Institut für Integrierte Naturwissenschaften, Abt. Chemie (2)
- Institut für Pädagogik, Abteilung Schulpädagogik/Allgemeine Didaktik (2)
- Institut für Softwaretechnik (2)
- Fachbereich 5 (1)
- Institut für Germanistik (1)
- Institut für Integrierte Naturwissenschaften (1)
- Institut für Integrierte Naturwissenschaften, Abt. Physik (1)
- Institut für Kulturwissenschaft (1)
- Institut für Kunstwissenschaft (1)
- Institut für Management (1)
- Institut für Pädagogik, Abteilung Pädagogik (1)
- Institut für Sozialwissenschaften (1)
- Institut für Sportwissenschaft (1)
- Institut für Umweltwissenschaften (1)
- Institut für Wirtschafts- und Verwaltungsinformatik (1)
- Mathematisches Institut (1)
Absicherung der analytischen Interpretation von Geolokalisierungsdaten in der Mobilfunkforensik
(2019)
Abstract
Location based services maybe are within one of the most outstanding features of modern mobile devices. Despite the fact, that cached geolocation data could be used to reconstruct motion profiles, the amount of devices capable to provide these information in the field of criminal investigations is growing.
Motivation
The aim of this work is to generate in-depth knowledge to questions concerning geolocation in the field of mobile forensics, making especially somehow cached geolocation data forensically valuable. On top, tools meeting the specific requirements of law enforcement personnel shall be developed.
Problems
Geolocation processes within smartphones are quite complex. For the device to locate its position, different reference systems like GPS, cell towers or WiFi hot\-spots are used in a variety of ways. The whole mobile geolocation mechanism is proprietary to the device manufacturer and not build with forensic needs in mind. One major problem regarding forensic investigations is, that mainly reference points are being extracted and processed instead of real life device location data. In addition, these geolocation information only consist of bits and bytes or numeric values that have to be securely assigned to their intended meaning. The location data recovered are full of gaps providing only a part of the process or device usage. This possible loss of data has to be determined deriving a reliable measurement for the completeness, integrity and accuracy of data. Last but not least, as for every evidence within a criminal investigation, it has to be assured, that manipulations of the data or errors in position estimation have no disadvantageous effect on the analysis.
Research Questions
In the context of localisation services in modern smartphones, it always comes back to similar questions during forensic everyday life:
* Can locations be determined at any time?
* How accurate is the location of a smartphone?
* Can location data from smartphones endure in court?
Approach
For a better understanding of geolocation processes in modern smartphones and to evaluate the quality and reliability of the geolocation artefacts, information from different platforms shall be theoretically analysed as well as observed in-place during the geolocation process. The connection between data points and localisation context will be examined in predefined live experiments as well as desktop- and native applications on smartphones.
Results
Within the scope of this thesis self developed tools have been used for forensic investigations as well as analytical interpretation of geodata from modern smartphones. Hereby a generic model for assessing the quality of location data has emerged, which can be generally applied to geodata from mobile devices.
Die Nachhaltigkeitsberichterstattung kann als ein zentrales Element einer konsequenten Unternehmensstrategie zur Umsetzung der gesellschaftlichen Verantwortung (Corporate Social Responsibility) angesehen werden. Um die Unternehmen bei dieser Aufgabe zu unterstützen stellt die Global Reporting Initiative (GRI) mit ihren G4 Leitlinien einen Orientierungsrahmen bereit, dessen Anwendung sich allerdings für Klein und Mittelunternehmen sehr komplex gestaltet. Ein branchenspezifisches Sector Supplement für den Weinbau existiert derzeit noch nicht.
Ziel der vorliegenden Arbeit ist es, diese Forschungslücke durch die Entwicklung weinbauspezifischer Nachhaltigkeitsaspekte und Indikatoren zu schließen, um den Betrieben eine selbstständige GRI-konforme Berichterstattung zu ermöglichen.
Der Prozess zur Identifikation wesentlicher Nachhaltigkeitsaspekte und -indikatoren erfolgt mittels Erhebungs- und Auswertungsmethoden der qualitativen Sozialforschung in Form
von Workshops, betrieblichen Vorortanalysen und Experteninterviews.
Parallel dazu erfolgt eine umfassende Analyse der weinbaulichen Wertschöpfungskette in Form einer Internet- und Literaturrecherche. Diese umfasst vorrangig die ökologischen Nachhaltigkeitsaspekte als diejenigen Bestandteile weinbaulicher Tätigkeiten, die sich sowohl positiv als auch negativ auf die Umwelt auswirken können. Anschließend erfolgt die zentrale Priorisierung der identifizieren Handlungsfelder und Nachhaltigkeitsthemen durch die Stakeholder. Zur Visualisierung der bewerteten Handlungsfelder dient das Instrument der Wesentlichkeitsanalyse.
Auf dieser Basis erfolgt die Entwicklung eines Handlungsleitfadens zur Erstellung von Nachhaltigkeitsberichten in der Weinwirtschaft. Hiermit erlangen Weingüter die praktische Kompetenz ein eigenes Nachhaltigkeitsreporting anzugehen.
Im Rahmen der Arbeit wurde auch ein elektronisches Tool entwickelt, das den Betrieben die Möglichkeit eröffnet, betriebliche Umweltaspekte zu erfassen und zu bewerten. Gleichzeitig wird den Anwendern damit die Generierung eines überbetrieblichen Vergleichs der Umweltleistung ermöglicht (Benchmarking).
Eine weitere Forschungsfrage der vorliegenden Arbeit beschäftigt sich mit der Biodiversitätserfassung und -bewertung für Rebland. Hintergrund sind die bisher nur geringen Funde auf der durch das Bundesamt für Naturschutz festgelegten Kennartenlisten bzw. den HNV-Stichprobenflächen (High nature value farmland-Indikator) für Rebland.
Hierzu wurde mittels Geoinformationssystemen das Artenvorkommen in rheinland-pfälzischen Weinanbaugebieten analysiert und 30 Pflanzenarten als Indikatorarten für den Weinbau abgeleitet. Ergänzend wurden weinbergstypische, geschützte Tierarten als „Bonusarten“ identifiziert. Die Indikatorarten werden den Winzern als ein Instrument zur eigenständigen Erfassung der Biodiversität in den Weinbergen dienen und im Rahmen einer Nachhaltigkeitsberichterstattung herangezogen werden können.
Streams are coupled with their riparian area. Emerging insects from streams can be an important prey in the riparian area. Such aquatic subsidies can cause predators to switch prey or increase predator abundances. This can impact the whole terrestrial food web. Stressors associated with agricultural land use can alter insect communities in water and on land, resulting in complex response patterns of terrestrial predators that rely on prey from both systems.
This thesis comprises studies on the impact of aquatic nsects on a terrestrial model ecosystem (Objective 1, hapter 2), the influence of agricultural land use on riparian spiders’ traits and community (Objective 2, Chapter 3), and on the impact of agricultural land use on the contribution of different prey to spider diet (Objective 3, Chapter 4).
In chapter 2, I present a study where we conducted a mesocosm experiment to examine the effects of aquatic subsidies on a simplified terrestrial food web consisting of two types of herbivores (leafhoppers and weevils), plants and predators (spiders). I focused on the prey choice of the spiders by excluding predator immigration and reproduction. In accordance with predator switching, survival of leafhoppers increased in the presence of aquatic subsidies. By contrast, the presence of aquatic subsidies indirectly reduced weevils and herbivory.
In chapter 3, I present the results on the taxonomic and trait response of riparian spider communities to gradients of agricultural stressors and environmental variables, with a particular emphasis on pesticides. To capture spiders with different traits and survival strategies, we used multiple collection methods. Spider community composition was best explained by in-stream pesticide toxicity and shading of the stream bank, a proxy for the quality of the habitat. Species richness and the number of spider individuals, as well as community ballooning ability, were negatively associated with in-stream pesticide toxicity. In contrast, mean body size and shading preference of spider communities responded strongest to shading,
whereas mean niche width (habitat preference for moisture and shading) responded strongest to other environmental variables.
In chapter 4, I describe aquatic-terrestrial predator-prey relations with gradients of agricultural stressors and environmental variables. I sampled spiders, as well as their aquatic and terrestrial prey along streams with an assumed pesticide pollution gradient and determined their stable carbon and nitrogen signals. Potential aquatic prey biomass correlated positively with an increasing aquatic prey contribution of T. montana. The contribution of aquatic prey to the diet of P. amentata showed a positive relationship with increasing toxicity in streams.
Overall, this thesis contributes to the emerging discipline of cross-ecosystem ecology and shows that aquatic-terrestrial linkages and riparian food webs can be influenced by land use related stressors. Future manipulative field studies on aquatic-terrestrial linkages are required that consider the quality of prey organisms, fostering mechanistic understanding of such crossecosystem effects. Knowledge on these linkages is important to improve understanding of consequences of anthropogenic stressors and to prevent further losses of ecosystems and their biodiversity.
Groundwater is essential for the provision of drinking water in many areas around the world. The ecosystem services provided by groundwater-related organisms are crucial for the quality of groundwater-bearing aquifers. Therefore, if remediation of contaminated groundwater is necessary, the remediation method has to be carefully selected to avoid risk-risk trade-offs that might impact these valuable ecosystems. In the present thesis, the ecotoxicity of the in situ remediation agent Carbo-Iron (a composite of zero valent nano-iron and active carbon) was investigated, an estimation of its environmental risk was performed, and the risk and benefit of a groundwater remediation with Carbo-Iron were comprehensively analysed.
At the beginning of the work on the present thesis, a sound assessment of the environmental risks of nanomaterials was impeded by a lack of guidance documents, resulting in many uncertainties on selection of suitable test methods and a low comparability of test results from different studies with similar nanomaterials. The reasons for the low comparability were based on methodological aspects of the testing procedures before and during the toxicity testing. Therefore, decision trees were developed as a tool to systematically decide on ecotoxicity test procedures for nanomaterials. Potential effects of Carbo-Iron on embryonic, juvenile and adult life stages of zebrafish (Danio rerio) and the amphipod Hyalella azteca were investigated in acute and chronic tests. These tests were based on existing OECD and EPA test guidelines (OECD, 1992a, 2013a, 2013b; US EPA, 2000) to facilitate the use of the obtained effect data in the risk assessment. Additionally, the uptake of particles into the test organisms was investigated using microscopic methods. In zebrafish embryos, effects of Carbo-Iron on gene expression were investigated. The obtained ecotoxicity data were complemented by studies with the waterflea Daphnia magna, the algae Scenedesmus vacuolatus, larvae of the insect species Chironomus riparius and nitrifying soil microorganisms.
In the fish embryo test, no passage of Carbo-Iron particles into the perivitelline space or the embryo was observed. In D. rerio and H. azteca, Carbo-Iron was detected in the gut at the end of exposure, but no passage into the surrounding tissue was detected. Carbo-Iron had no significant effect on soil microorganisms and on survival and growth of fish. However, it had significant effects on the growth, feeding rate and reproduction of H. azteca and on survival and reproduction in D. magna. Additionally, the development rate of C. riparius and the cell volume of S. vacuolatus were negatively influenced.
A predicted no effect concentration of 0.1 mg/L was derived from the ecotoxicity studies based on the no-effect level determined in the reproduction test with D. magna and an assessment factor of 10. It was compared to measured and modelled environmental concentrations for Carbo-Iron after application to an aquifer contaminated with chlorohydrocarbons in a field study. Based on these concentrations, risk quotients were derived. Additionally, the overall environmental risk before and after Carbo-Iron application was assessed to verify whether the chances for a risk-risk trade-off by the remediation of the contaminated site could be minimized. With the data used in the present study, a reduced environmental risk was identified after the application of Carbo-Iron. Thus, the benefit of remediation with Carbo-Iron outweighs potential negative effects on the environment.
In this thesis, I present the results of my studies on taxonomy, systematics, and biogeography of Impatiens (Balsaminaceae) in Madagascar and the Comoro islands.
In Chapter 1 I reviewed the literature on taxonomy and classification of Balsaminaceae, on habitat, world distribution, morphology, molecular phylogenetics and infrageneric classification of the genus Impatiens. In Chapters 2-15 (Fischer & Rahelivololona 2002, 2003, 2004, 2007, 2015a, 2015b, 2015c, 2016, Fischer et al. 2004. 2017, 2018a, b submitted, Rahelivololona et al. 2003) I presented the first results of a revision of Balsaminaceae of Madagascar and the Comoro islands including the description of 78 new species. In Chapter 16 (Yuan et al. 2004) we worked on the phylogeny and biogeography of Balsaminaceae inferred from ITS sequences using combined results from molecular phylogenetic and morphological analyses. In Chapter 17 (Rahelivololona et al. 2018) we conducted a phylogeny and assessment of the infrageneric classification of species in the Malagasy Impatiens (Balsaminaceae) with a particular emphasis on taxa collected from Marojejy.
Below I summarise the most important findings of each chapter and provide an outlook for future studies.
How many species of Impatiens occur in Madagascar and the Comoro islands?
To provide additional information on the taxonomic revision of Impatiens in Madagascar and the Comoro islands, the identification of already described species as well as the description of new species was conducted. Based on herbarium specimens from BR, G, K, NEU, P, TAN and on living plants collected during several field trips, 78 new species and 6 nomina nova have been published and another 70 new taxa are already identified. Actually more than 260 species occur in Madagascar and the Comoro islands and all of them are endemic. For each species, a description of the morphology, phenology, ecology and known distribution range was provided. Apart from new taxa, the delimitation of already described species like Impatiens firmula Baker and Impatiens hildebrandtii Baill. could be clarified by studying the types and by observing the variability in the field.
Are the groups of Impatiens in Madagascar monophyletic, and what is the systematic position of Trimorphopetalum?
Yuan & al. (2004) conducted a molecular phylogenetic study to examine the morphological and karyological evolution, and the historical biogeography of the Balsaminaceae family by using nucleotide sequence data of internal transcribed spacer regions of nuclear ribosomal DNA. The results support the monophyly of the Malagasy endemic section Trimorphopetalum and show that the cleistogamous Impatiens inaperta should be included in the sect. Trimorphopetalum which is the most derived within Impatiens. Therefore, the section Preimpatiens proposed by Perrier de la Bâthie (1934) is paraphyletic.
Rahelivololona & al. (2018) provided a phylogenetic study focused on three subdivisions (based on macromorphological characters) proposed by Perrier de la Bâthie (1934). The analysis was done using two nuclear AP3/DEF homologues (ImpDEF1 and ImpDEF2) and the plastid atpB-rbcL spacer to reassess or assess the monophyly of the Malagasy Impatiens, of the sections Preimpatiens (Humblotianae and Vulgare groups) and Trimorphopetalum. A focus was on the species of Impatiens from the Marojejy National Park and of the morphologically variable species I. elatostemmoides, I. “hammarbyoides”, I. inaperta and I. manaharensis, using monophyly as the primary criterion.
As results the Malagasy Impatiens are paraphyletic and the section Preimpatiens sensu Perrier de la Bâthie (1934) (= subgen. Impatiens sensu Fischer & Rahelivololona 2002) was not resolved as a monophyletic group. The section Trimorphopetalum sensu Perrier de la Bâthie (1934) (= subgen. Trimorphopetalum sensu Fischer & Rahelivololona 2002), however, was strongly confirmed as a monophyletic lineage (BS: 92; BPP: 1). Neither the Humblotianae group nor the Vulgare group was supported as monophyletic. None of the morphologically variable species appeared to be monophyletic and the sampled species of Impatiens from the Marojejy National Park do also not form a monophyletic group.
What are the biogeographical position and the distribution patterns of Impatiens in Madagascar and the Comoro islands?
Investigation of the geographical affinities and species distribution of section Impatiens (including Humblotianae group and Vulgare group) and section Trimorphopetalum were conducted and the origin and evolution as well as species richness and endemism were discussed.
The isolation, the climate and the complex topography of Madagascar have generated the microhabitats and ecological niches favourable to the diversification of Impatiens species. Impatiens of Madagascar with 260 endemic species is actually the largest genus in Madagascar. Therefore, Madagascar and the Comoro islands are among the most species-rich regions in the world for Impatiens.
Future studies
In Impatiens on Madagascar, there remain numerous unresolved questions that need to be adressed:
• A further study based on a much larger molecular data set and sampling from the entire geographic ranges of Impatiens in Madagascar is needed to retest the monophyly of the different subgenera and sections, as well as a molecular dating of the Malagasy Impatiens.
• The study of pollinators as a key for understanding the radiation and species richness is required: Within Impatiens the different shapes of spur are related to pollinators (bees, birds, butterflies and moths). Therefore pollinator observation of specific species need to be done to understand the radiation of species by adaptation and coevolution with these pollinators. A pollination study with a large number of species within section Trimorphopetalum will help to understand the mechanism of complete disappearance of the spur, the shift of pollinators and the evolution of species richness.
• The destruction of the natural habitats of Impatiens and the subsequent reduction of humidity in logged area constitute a severe threat for the survival of many species. The conservation and reforestation of vulnerable areas such as Ankaratra, Daraina, Mandraka and Col des Tapia near Antsirabe is required.
• In terms of conservation and to mitigate the threat on the genus, a study on the ex-situ-conservation of Malagasy Impatiens species is very important as long as some species are suitable for horticultural purposes (e.g. Impatiens mayae-valeriae, Impatiens emiliae and species with broad red spur).
• Finally, the publication of the revision of Impatiens of Madagascar and the Comoro islands will help other botanists to identify the species and will thus increase our knowledge on the group.
Sediment transport contributes to the movement of inorganic and organic material in rivers. The construction of a dam interrupts the continuity of this sediment transport through rivers, causing sediments to accumulate within the reservoir. Reservoirs can also act as carbon sinks and methane can be released when organic matter in the sediment is degraded under anoxic conditions. Reservoir sedimentation poses a great threat to the sustainability of reservoirs worldwide, and can emit the potent greenhouse gas methane into the atmosphere. Sediment management measures to rehabilitate silted reservoirs are required to achieve both better water quantity and quality, as well as to mitigate greenhouse gas emissions.
This thesis aims at the improvement of sediment sampling techniques to characterize sediment deposits as a basis for accurate and efficient water jet dredging and to monitor the dredging efficiency by measuring the sediment concentration. To achieve this, we investigated freeze coring as a method to sample (gas-bearing) sediment in situ. The freeze cores from three reservoirs obtained were scanned using a non-destructive X-Ray CT scan technique. This allows the determination of sediment stratification and character-ization of gas bubbles to quantify methane emissions and serve as a basis for the identi-fication of specific (i.e. contaminated) sediment layers to be dredged. The results demon-strate the capability of freeze coring as a method for the characterization of (gas-bearing) sediment and overcomes certain limitations of commonly used gravity cores. Even though the core’s structure showed coring disturbances related to the freezing process, the general core integrity seems to not have been disturbed. For dredging purposes, we analyzed the impact pressure distribution and spray pattern of submerged cavitating wa-ter jets and determined the effects of impinging distances and angles, pump pressures and spray angles. We used an adapted Pressure Measurement Sensing technique to enhance the spatial distribution, which proved to be a comparatively easy-to-use meas-urement method for an improved understanding of the governing factors on the erosional capacity of cavitating water jets. Based on this data, the multiple linear regression model can be used to predict the impact pressure distribution of those water jets to achieve higher dredging accuracy and efficiency. To determine the dredging operational efficien-cy, we developed a semi-continuous automated measurement device to measure the sediment concentration of the slurry. This simple and robust device has lower costs, compared to traditional and surrogate sediment concentration measurement technolo-gies, and can be monitored and controlled remotely under a wide range of concentrations and grain-sizes, unaffected by entrained gas bubbles
While the existing literature on cooperative R&D projects between firms and public research institutes (PRI) has made valuable contributions by examining various factors and their influence on different outcome measures, there has been no investigation of cooperative R&D project success between firms and PRI from a product competitive advantage perspective. However, insights into the development of a meaningful and superior product (i.e., product competitive advantage) are particularly important in the context of cooperative R&D projects between PRI and (mainly small and medium-sized) firms in the biotechnology industry in response to increasing competition to raise capital funds necessary for survival.
The objectives of this thesis are: (1) to elaborate the theoretical foundations which explain the achievement of a product competitive advantage in cooperative R&D projects between biotechnology firms and PRI, (2) to identify and empirically evaluate the determining factors for achieving a product competitive advantage in cooperative R&D projects between biotechnology firms and PRI, and (3) to show how cooperative R&D projects between biotechnology firms and PRI should be designed and executed to support the achievement of a product competitive advantage.
To accomplish these objectives, a model of determinants of product competitive advantage in cooperative R&D projects between biotechnology firms and PRI is developed by drawing from the theoretical foundations of resource-based theory and information-processing theory. The model is evaluated using data from 517 questionnaires on cooperative R&D projects between at least one biotechnology firm and one PRI. The data are analyzed using variance-based structural equation modeling (i.e., PLS-SEM) in order to conduct hypotheses testing. The evaluation of the empirical data includes an additional mediation analysis and the comparison of effects in subsamples.
The results demonstrate the importance of available resources and skills, as well as the proficient execution of marketing-related and technical activities for the achievement of a product competitive advantage in cooperative R&D projects between biotechnology firms and PRI. By identifying project-related and process-related factors affecting product competitive advantage and empirically testing their relationships, the research findings should be valuable for both researchers and practitioners. After discussing contributions and implications for research and practice, the present thesis concludes with limitations and avenues for future research.
Ecological assessment approaches based on benthic invertebrates in Euphrates tributaries in Turkey
(2019)
Sustainable water management requires methods for assessing ecological stream quality. Many years of limnological research are needed to provide a basis for developing such methods. However, research of this kind is still lacking in Turkey. Therefore, the aim of this doctoral thesis was to provide basic research in the field of aquatic ecology and to present methods for the assessment of ecological stream quality based on benthic invertebrates. For this purpose, I selected 17 tributaries of the Euphrates with a similar typology/water order and varying levels of pollution or not affected by pollution at all. The characterisation of the natural mountain streams was the first important step in the analysis of ecological quality. Based on community indices, I found that the five selected streams had a very good ecological status. I also compared the different biological indications, collected on two occasions ¬– once in spring (May) and once in autumn (September) – to determine the optimal sampling time. The macroinvertebrate composition differed considerably between the two seasons, with the number of taxa and Shannon index being significantly higher in autumn than in spring. In the final step, I examined the basal resources of the macroinvertebrates in the reference streams with an isotope analysis. I found that FPOM and biofilm were the most relevant basal resources of benthic invertebrates. Subsequently, based on the similarity of their community structures, I divided the 17 streams into three quality classes, supported by four community indices (EPT [%], EPTCBO [%], number of individuals, evenness). In this process, 23 taxa were identified as indicators for the three quality classes. In the next step, I presented two new or adapted indices for the assessment of quality class. Firstly, I adapted the Hindu Kush-Himalaya biotic index to the catchment area of the Euphrates and created a new, ecoregion-specific score list (Euph-Scores) for 93 taxa. The weighted ASPT values, which were renamed the Euphrates Biotic Score (EUPHbios) in this study, showed sharper differentiations of quality classes compared to the other considered ASPT values. Thus, this modified index has proved to be very effective and easy to implement in practical applications. As a second biological index, I suggested the proportion of habitat specialists. To calculate this index, the habitat preferences of the 20 most common benthic invertebrates were identified using the new habitat score. The proportion of habitat specialists differed significantly among the three quality classes with higher values in natural streams than in polluted streams. The methods and results presented in this doctoral thesis can be used in a multi-metric index for a Turkish assessment programme.
In the present dissertation, the structural interaction between potassium waterglass and aluminium metaphosphates (aluminium tetrametaphosphate and aluminium hexametaphosphate) were investigated in terms of the resettlement behaviour of the metaphosphates as hardening agents. The crystalline phase composition was described qualitatively and quantitatively in terms of powder diffraction patterns combined with Rietveld refinement. The amorphous phase content was determined by different spectroscopic methods (e.g. solid-state NMR, ATR-IR, and Raman spectroscopy). The solubility behaviour of the chemical hardening agents was investigated by optical emission spectroscopy and electron absorption spectroscopy. The mechanical properties of the samples were measured by three-point bending tests, resonance damping frequency analysis, and acid test. The structural framework of the chemically hardened waterglasses was explored by scanning electron microscopy method. It could be proven, that the reaction mechanism of the resettlement is strongly dependent on the structure of the aluminium metaphosphate. After the dissolution of the aluminium ions of aluminium tetrametaphosphate through the alkalic environment of the potassium waterglass, a potassium tetrametaphosphate is developed through an ion-exchange reaction with the waterglass` potassium ions. In the hexametaphosphate system, no analogous structure could be proven. Parallel to the ion-exchange reaction an incremental depolymerization of the cyclic metaphosphate structure to the final crystalline product potassium dihydrogen phosphate occurs. The drop in pH value due to the addition of the respective aluminium metaphosphate initiates a polycondensation of the potassium waterglass due to the decreasing stabilization of the waterglass. This process is increased by the depolymerization products of the metaphosphate, that remove further quantities of the alkali ions, which accelerates the polycondensation reaction due to a further decrease in pH value. The dissolved aluminium ions from the aluminium metaphosphate penetrate into the amorphous, hardening silica network and develops an alumosilicate binder matrix. Furthermore, amorphous hydrated aluminium phosphate phases develop in separate domains beside silicate, alumosilicate phases, and the crystalline phase contents e.g. potassium dihydrogenphosphate and the incomplete reacted aluminium metaphosphate. Consequently, the chemically hardened potassium waterglass binder is not necessarily homogenous. Regarding the mechanical and chemical properties, in summary with increasing alkali modulus the mechanical flexural strength, and the young modulus drop, while the chemical resistance towards acid attack, and the porosity of the samples increase. The change in the cyclic structure from aluminium tetrametaphosphate to aluminium hexametaphosphate leads to a drop in the acid resistance, the porosity of the samples, the flexural strength, and the young modulus.
Refractory dry-vibratable mixes, which consist of a mineral filling material and an organic or anorganic binder system, are widely used for linings in industrial aggregates, where a very high temperature resistance is required (e.g. steel industry). During lining, all compounds are mixed and hardening is chemically or thermally initiated. The time span required for hardening is of special relevance for the application of refractory dry-vibratable mixes. It should be long enough for adequate processability, but simultaneously avoid too long downtimes. Prediction or regulation of the hardening time, necessary for an ideal processing, is currently limited. One the one hand, this is a result of the lack of an appropriate method for time-dependent determination of the harding process. On the other hand, the mechanisms responsible for this very complex process have not yet been investigated in detail and the effect of influencing factors, like the temperature or the composition of the refractory dry-vibratable mixes, are poorly documented.
To make a contribution to the understanding of the hardening mechanism of refractory dry-vibratable mixes, it was the aim of the present work, to develop an appropriate test method for the time-dependent investigation of this process. This was realized by means of the dynamic-mechanical analysis. In addition, the hardening mechanism was described for a refractory dry-vibratable mix with a binder system, which consists of a waterglass and a phosphate hardener (AlPO4 und BPO4), using supplement gravimetric investigations and determining solubility behavior of the phosphates. By means of X-ray diffraction analysis, nuclear magnetic resonance spectroscopy and scanning electron microscopy, the impact of the hardening mechanism on the crystal and amorphous structure was studied. It could be shown, that according to the two phosphates, the hardening leads to different network structures in respect of their link denseness. These structure characteristics correlate with the speed of the hardening reactions. In addition, the impact on selected properties (thermal linear deformation, temperature-dependent phase development and phase transition) could be deducted.