Behavior of geopolymer concrete exposed to elevated temperatures

The research in the area of geopolymer is gaining momentum during the past 20 years. Studies confirm that geopolymer concrete has good compressive strength, tensile strength, flexural strength, modulus of elasticity and durability. These properties are comparable with OPC concrete.There are many occasions where concrete is exposed to elevated temperatures like fire exposure from thermal processor, exposure from furnaces, nuclear exposure, etc.. In such cases, understanding of the behaviour of concrete and structural members exposed to elevated temperatures is vital. Even though many research reports are available about the behaviour of OPC concrete at elevated temperatures, there is limited information available about the behaviour of geopolymer concrete after exposure to elevated temperatures. A preliminary study was carried out for the selection of a mix proportion. The important variable considered in the present study include alkali/fly ash ratio, percentage of total aggregate content, fine aggregate to total aggregate ratio, molarity of sodium hydroxide, sodium silicate to sodium hydroxide ratio, curing temperature and curing period. Influence of different variables on engineering properties of geopolymer concrete was investigated. The study on interface shear strength of reinforced and unreinforced geopolymer concrete as well as OPC concrete was also carried out. Engineering properties of fly ash based geopolymer concrete after exposure to elevated temperatures (ambient to 800 °C) were studied and the corresponding results were compared with those of conventional concrete. Scanning Electron Microscope analysis, Fourier Transform Infrared analysis, X-ray powder Diffractometer analysis and Thermogravimetric analysis of geopolymer mortar or paste at ambient temperature and after exposure to elevated temperature were also carried out in the present research work. Experimental study was conducted on geopolymer concrete beams after exposure to elevated temperatures (ambient to 800 °C). Load deflection characteristics, ductility and moment-curvature behaviour of the geopolymer concrete beams after exposure to elevated temperatures were investigated. Based on the present study, major conclusions derived could be summarized as follows. There is a definite proportion for various ingredients to achieve maximum strength properties. Geopolymer concrete with total aggregate content of 70% by volume, ratio of fine aggregate to total aggregate of 0.35, NaOH molarity 10, Na2SiO3/NaOH ratio of 2.5 and alkali to fly ash ratio of 0.55 gave maximum compressive strength in the present study. An early strength development in geopolymer concrete could be achieved by the proper selection of curing temperature and the period of curing. With 24 hours of curing at 100 °C, 96.4% of the 28th day cube compressive strength could be achieved in 7 days in the present study. The interface shear strength of geopolymer concrete is lower to that of OPC concrete. Compared to OPC concrete, a reduction in the interface shear strength by 33% and 29% was observed for unreinforced and reinforced geopolymer specimens respectively. The interface shear strength of geopolymer concrete is lower than ordinary Portland cement concrete. The interface shear strength of geopolymer concrete can be approximately estimated as 50% of the value obtained based on the available equations for the calculation of interface shear strength of ordinary portland cement concrete (method used in Mattock and ACI). Fly ash based geopolymer concrete undergoes a high rate of strength loss (compressive strength, tensile strength and modulus of elasticity) during its early heating period (up to 200 °C) compared to OPC concrete. At a temperature exposure beyond 600 °C, the unreacted crystalline materials in geopolymer concrete get transformed into amorphous state and undergo polymerization. As a result, there is no further strength loss (compressive strength, tensile strength and modulus of elasticity) in geopolymer concrete, whereas, OPC concrete continues to lose its strength properties at a faster rate beyond a temperature exposure of 600 °C. At present no equation is available to predict the strength properties of geopolymer concrete after exposure to elevated temperatures. Based on the study carried out, new equations have been proposed to predict the residual strengths (cube compressive strength, split tensile strength and modulus of elasticity) of geopolymer concrete after exposure to elevated temperatures (upto 800 °C). These equations could be used for material modelling until better refined equations are available. Compared to OPC concrete, geopolymer concrete shows better resistance against surface cracking when exposed to elevated temperatures. In the present study, while OPC concrete started developing cracks at 400 °C, geopolymer concrete did not show any visible cracks up to 600 °C and developed only minor cracks at an exposure temperatureof 800 °C. Geopolymer concrete beams develop crack at an early load stages if they are exposed to elevated temperatures. Even though the material strength of the geopolymer concrete does not decrease beyond 600 °C, the flexural strength of corresponding beam reduces rapidly after 600 °C temperature exposure, primarily due to the rapid loss of the strength of steel. With increase in temperature, the curvature at yield point of geopolymer concrete beam increases and thereby the ductility reduces. In the present study, compared to the ductility at ambient temperature, the ductility of geopolymer concrete beams reduces by 63.8% at 800 °C temperature exposure. Appropriate equations have been proposed to predict the service load crack width of geopolymer concrete beam exposed to elevated temperatures. These equations could be used to limit the service load on geopolymer concrete beams exposed to elevated temperatures (up to 800 °C) for a predefined crack width (between 0.1mm and 0.3 mm) or vice versa. The moment-curvature relationship of geopolymer concrete beams at ambient temperature is similar to that of RCC beams and this could be predicted using strain compatibility approach Once exposed to an elevated temperature, the strain compatibility approach underestimates the curvature of geopolymer concrete beams between the first cracking and yielding point.

Mikrostrukturierte Sensoren für die pH-Wert-Bestimung auf Basis von dünnen, intrinisch leitfähigen Polyanilinschichten

Der pH-Wert stellt in der Chemie, Physik, Biologie, Pharmazie und Medizin eine wichtige Meßgröße dar, da eine Vielzahl von Reaktionen durch den pH-Wert bestimmt wird. In der Regel werden zur pH-Wert-Messung Glaselektroden eingesetzt. Hierbei konnte der pH-sensitive Bereich zwar bis auf einige Mikrometer reduziert werden, aber die Gesamtab-messungen betragen immer noch 15-20 cm. Mit der Einführung miniaturisierter Reaktionsgefäße ist daher der Bedarf an miniaturisierten Sensoren enorm gestiegen. Um in solchen Gefäßen Reaktionsparameter wie z. B. den pH-Wert zu kontrollieren, müssen die Gesamtabmessungen der Sensoren verringert werden. Dies lässt sich mit Hilfe der Mikrostrukturtechnik von Silizium realisieren. Hiermit lassen sich Strukturen und ganze Systeme bis in den Nanometerbereich herstellen. Basierend auf Silizium und Gold als Elektrodenmaterial wurden im Rahmen dieser Arbeit verschiedene Interdigitalstrukturen hergestellt. Um diese Strukturen zur pH-Wert-Messungen einsetzen zu können, müssen sie mit einer pH-sensitiven Schicht versehen werden. Hierbei wurde Polyanilin, ein intrinsisch leitendes Polymer, aufgrund seine pH-abhängigen elektrischen und optischen Verhaltens eingesetzt. Die Beschichtung dieser Sensoren mit Polyanilin erfolgte vorwiegend elektrochemisch mit Hilfe der Zyklovoltammetrie. Neben der Herstellung reiner Polyanilinfilme wurden auch Kopolymerisationen von Anilin und seinen entsprechenden Aminobenzoesäure- bzw. Aminobenzensulfonsäurederivaten durchgeführt. Ergebnisse dazu werden vorgestellt und diskutiert. Zur Charakterisierung der resultierenden Polyanilin- und Kopolymerfilme auf den Inter-digitalstrukturen wurden mit Hilfe der ATR-FT-IR-Spektroskopie Spektren aufgenommen, die gezeigt und diskutiert werden. Eine elektrochemische Charakterisierung der Polymere erfolgte mittels der Zyklovoltammetrie. Die mit Polyanilin bzw. seinen Kopolymeren beschichteten Sensoren wurden dann für Widerstandsmessungen an den Polymerfilmen in wässrigen Medien eingesetzt. Polyanilin zeigt lediglich eine pH-Sensitivität in einem pH-Bereich von pH 2 bis pH 4. Durch den Einsatz der Kopolymere konnte dieser pH-sensitive Bereich jedoch bis zu einem pH-Wert von 10 ausgeweitet werden. Zur weiteren Miniaturisierung der Sensoren wurde das Konzept der interdigitalen Elektroden-paare auf Cantilever übertragen. Die pH-sensitive Zone konnte dabei auf 500 µm2 bei einer Gesamtlänge des Sensors (Halter mit integriertem Cantilever) von 4 mm reduziert werden. Neben den elektrischen pH-abhängigen Eigenschaften können auch die optischen Eigen-schaften des Polyanilins zur pH-Detektion herangezogen werden. Diese wurden zunächst mit Hilfe der UV-VIS-Spektroskopie untersucht. Die erhaltenen Spektren werden gezeigt und kurz diskutiert. Mit Hilfe eines Raster-Sonden-Mikroskops (a-SNOM, Firma WITec) wurden Reflexionsmessungen an Polyanilinschichten durchgeführt. Zur weiteren Miniaturisierung wurden Siliziumdioxidhohlpyramiden (Basisfläche 400 µm2) mit Spitzenöffnungen in einem Bereich von 50-150 nm mit Polyanilin beschichtet. Auch hier sollten die optischen Eigenschaften des Polyanilins zur pH-Wert-Sensorik ausgenutzt werden. Es werden erste Messungen an diesen Strukturen in Transmission diskutiert.

Femtosecond imaging-mode laser-induced breakdown spectroscopy

Many nonlinear optical microscopy techniques based on the high-intensity nonlinear phenomena were developed recent years. A new technique based on the minimal-invasive in-situ analysis of the specific bound elements in biological samples is described in the present work. The imaging-mode Laser-Induced Breakdown Spectroscopy (LIBS) is proposed as a combination of LIBS, femtosecond laser material processing and microscopy. The Calcium distribution in the peripheral cell wall of the sunflower seedling (Helianthus Annuus L.) stem is studied as a first application of the imaging-mode LIBS. At first, several nonlinear optical microscopy techniques are overviewed. The spatial resolution of the imaging-mode LIBS microscope is discussed basing on the Point-Spread Function (PSF) concept. The primary processes of the Laser-Induced Breakdown (LIB) are overviewed. We consider ionization, breakdown, plasma formation and ablation processes. Water with defined Calcium salt concentration is used as a model of the biological object in the preliminary experiments. The transient LIB spectra are measured and analysed for both nanosecond and femtosecond laser excitation. The experiment on the local Calcium concentration measurements in the peripheral cell wall of the sunflower seedling stem employing nanosecond LIBS shows, that nanosecond laser is not a suitable excitation source for the biological applications. In case of the nanosecond laser the ablation craters have random shape and depth over 20 µm. The analysis of the femtosecond laser ablation craters shows the reproducible circle form. At 3.5 µJ laser pulse energy the diameter of the crater is 4 µm and depth 140 nm for single laser pulse, which results in 1 femtoliter analytical volume. The experimental result of the 2 dimensional and surface sectioning of the bound Calcium concentrations is presented in the work.

Wechselwirkung von im NANOJET erzeugten Teilchen mit Polymeren und biologischen Objekten

Am Institut für Mikrostrukturtechnologie und Analytik wurde eine neue Technik entwickelt, die neue Anwendungen und Methoden der Mikro- und Nanostrukturierung auf Basis eines neuen Verfahrens erschlossen hat. NANOJET führt über die passive Rastersondenmikroskopie hinaus zu einem vielseitigen, aktiven Bearbeitungswerkzeug auf der Mikro- und Nanometerskala. NANOJET (NANOstructuring Downstream PlasmaJET) ist eine aktive Rasterkraft-Mikroskopie-Sonde. Radikale (chemisch aktive Teilchen, die ein ungepaartes Valenzelektron besitzen) strömen aus dem Ende einer ultradünnen, hohlen Rasterkraftmikroskop-Spitze. Dadurch wird es möglich, über die übliche passive Abtastung einer Probenoberfläche hinausgehend, diese simultan und in-situ durch chemische Reaktionen zu verändern. Die Abtragung von Material wird durch eine chemische Ätzreaktion erreicht. In dieser Arbeit wurde zum größten Teil Photoresist als Substrat für die Ätzexperimente verwendet. Für das Ätzen des Resists wurden die Atome des Fluors und des Sauerstoffs im Grundzustand als verantwortlich identifiziert. Durch Experimente und durch Ergänzung von Literaturdaten wurde die Annahme bestätigt, dass Sauerstoffradikale mit Unterstützung von Fluorradikalen für die hohen erzielten Ätzraten verantwortlich sind. Die Beimischung von Fluor in einem Sauerstoffplasma führt zu einer Verringerung der Aktivierungsenergie für die Ätzreaktion gegenüber Verwendung reinen Sauerstoffs. In weiterer Folge wurde ein Strukturierungsverfahren dargestellt. Hierbei wurden "geformte Kapillaren" (mikrostrukturierte Aperturen) eingesetzt. Die Herstellung der Aperturen erfolgte durch einen elektrochemischen Ätzstop-Prozess. Die typische Größe der unter Verwendung der "geformten Kapillaren" geätzten Strukturen entsprach den Kapillarenöffnungen. Es wurde ein Monte-Carlo Simulationsprogramm entwickelt, welches den Transport der reaktiven Teilchen in der langen Transportröhre simulierte. Es wurde sowohl die Transmission der Teilchen in der Transportröhre und der Kapillare als auch ihre Winkelverteilung nach dem Verlassen der Kapillare berechnet. Das Aspektverhältnis der Röhren hat dabei einen sehr starken Einfluss. Mit einem steigenden Aspektverhältnis nahm die Transmission exponentiell ab. Die geschaffene experimentelle Infrastruktur wurde genutzt, um auch biologische Objekte zu behandeln und zu untersuchen. Hierfür wurde eine neue Methodik entwickelt, die eine dreidimensionale Darstellung des Zellinneren erlaubt. Dies wurde durch die kontrollierte Abtragung von Material aus der Zellmembran durchgeführt. Die Abtragung der Zellmembran erfolgte mittels Sauerstoffradikalen, die durch eine hohle Spitze lokalisiert zum Ort der Reaktion transportiert wurden. Ein piezoresistiver Cantilever diente als Sensor in dem zur Bildgebung eingesetzten RKM. Das entwickelte Verfahren ermöglicht es nun erstmals, schonend Zellen zu öffnen und die innen liegenden Organellen weiter zu untersuchen. Als Nachweis für weitere Verwendungsmöglichkeiten des NANOJET-Verfahrens wurde auch Knochenmaterial behandelt. Die Ergebnisse dieser Experimente zeigen klar, dass das Verfahren für vielfältige biologische Materialien verwendbar ist und somit nun ein weiter Anwendungskreis in der Biologie und Medizin offen steht.

Fliesslochformen und Gewindefurchen in dünne Bleche und Rohre aus Kupfer und Kupferlegierungen

This thesis in Thermal Flow Drilling and Flowtap in thin metal sheet and pipes of copper and copper alloys had as objectives to know the comportment of copper and copper alloys sheet metal during the Thermal Flow Drill processes with normal tools, to know the best Speed and Feed machine data for the best bushing quality, to known the best Speed for Form Tapping processes and to know the best bush long in pure copper pipes for water solar interchange equipment. Thermal Flow Drilling (TFD) and Form Tapping (FT) is one of the research lines of the Institute of Production and Logistics (IPL) at University of Kassel. At December 1995, a work meeting of IPL, Santa Catarina University, Brazil, Buenos Aires University, Argentine, Tarapacá University (UTA), Chile members and the CEO of Flowdrill B.V. was held in Brazil. The group decided that the Manufacturing Laboratory (ML) of UTA would work with pure copper and brass alloys sheet metal and pure copper pipes in order to develop a water interchange solar heater. The Flowdrill BV Company sent tools to Tarapacá University in 1996. In 1999 IPL and the ML carried out an ALECHILE research project promoted by the DAAD and CONICyT in copper sheet metal and copper pipes and sheet metal a-brass alloys. The normal tools are lobed, conical tungsten carbide tool. When rotated at high speed and pressed with high axial force into sheet metal or thin walled tube generated heat softens the metal and allows the drill to feed forward produce a hole and simultaneously form a bushing from the displacement material. In the market exist many features but in this thesis is used short and longs normal tools of TFD. For reach the objectives it was takes as references four qualities of the frayed end bushing, where the best one is the quality class I. It was used pure copper and a-brass alloys sheet metals, with different thickness. It was used different TFD drills diameter for four thread type, from M-5 to M10. Similar to the Aluminium sheet metals studies it was used the predrilling processes with HSS drills around 30% of the TFD diameter (1,5 – 3,0 mm D). In the next step is used only 2,0 mm thick metal sheet, and 9,2 mm TFD diameter for M-10 thread. For the case of pure commercial copper pipes is used for ¾” inch diameter and 12, 8 mm (3/8”) TFD drill for holes for 3/8” pipes and different normal HSS drills for predrilling processes. The chemical sheet metal characteristics were takes as reference for the material behaviour. The Chilean pure copper have 99,35% of Cu and 0,163% of Zinc and the Chilean a-brass alloys have 75,6% of Cu and 24,0% of Zinc. It is used two German a-brass alloys; Nº1 have 61,6% of Cu, 36,03 % of Zinc and 2,2% of Pb and the German a-brass alloys Nº2 have 63,1% of Cu, 36,7% of Zinc and 0% of Pb. The equipments used were a HAAS CNC milling machine centre, a Kistler dynamometer, PC Pentium II, Acquisition card, TESTPOINT and XAct software, 3D measurement machine, micro hardness, universal test machine, and metallographic microscope. During the test is obtained the feed force and momentum curves that shows the material behaviour with TFD processes. In general it is take three phases. It was possible obtain the best machining data for the different sheet of copper and a-brass alloys thick of Chilean materials and bush quality class I. In the case of a-brass alloys, the chemical components and the TFD processes temperature have big influence. The temperature reach to 400º Celsius during the TFD processes and the a-brass alloys have some percents of Zinc the bush quality is class I. But when the a-brass alloys have some percents of Lead who have 200º C melting point is not possible to obtain a bush, because the Lead gasify and the metallographic net broke. During the TFD processes the recrystallization structures occur around the Copper and a-brass alloy bush, who gives more hardness in these zones. When the threads were produce with Form Tapping processes with Flowtap tools, this hardness amount gives a high limit load of the thread when hey are tested in a special support that was developed for it. For eliminated the predrilling processes with normal HSS drills it was developed a compound tool. With this new tool it was possible obtain the best machining data for quality class I bush. For the copper pipes it is made bush without predrilling and the quality class IV was obtained. When it is was used predrilling processes, quality classes I bush were obtained. Then with different HSS drill diameter were obtained different long bush, where were soldering with four types soldering materials between pipes with 3/8” in a big one as ¾”. Those soldering unions were tested by traction test and all the 3/8” pipes broken, and the soldering zone doesn’t have any problem. Finally were developed different solar water interchange heaters and tested. As conclusions, the present Thesis shows that the Thermal Flow Drilling in thinner metal sheets of cooper and cooper alloys needs a predrilling process for frayed end quality class I bushings, similar to thinner sheets of aluminium bushes. The compound tool developed could obtain quality class I bushings and excludes predrilling processes. The bush recrystalization, product of the friction between the tool and the material, the hardness grows and it is advantageous for the Form Tapping. The methodology developed for commercial copper pipes permits to built water solar interchange heaters.

Development of hybrid UV VCSEL with organic active material and dielectric DBR mirrors for medical, sensoric and data storage applications

Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.

The Corticiaceae (Basidiomycetes) in Taiwan

Geographically, Taiwan is an Island and situated in the northeast of Asia, on the western side of the Pacific Basin, at the southeast of main China, south of Japan, and north of the Philippines. The main topographic character is the longitudinally oriented mountainous area. More than 200 peaks rise above 3000 m. They departed Taiwan into two lowland areas, an eastern and western plain. Taiwan is departed into subtropical (north area) and tropical zone (south area), which have a warm and humid climate, due to the Tropic of Cancer passing through. The average annual temperature in the lowland amounts to 28°C (7~38°C). The temperate climate also presents in the mountainous areas. The tropical typhoons usually come in summer and bring heavy rain, while the monsoon seasons have an important effect on the regional rainfall distribution. The mean annual rainfall of Taiwan is about 2600 mm (1000~6700 mm); the mountainous areas receive more rain than the lowlands. In Taiwan, according to different temperature and vegetation, the ecological environments were given rise to vertical biotic zonations, and form five major types: highland snowfield, highland meadow, coniferous forest, deciduous forest, and tropical forest. Six National Parks in Taiwan are located in the mountainous areas, in the north, the south, and on Jinmen Island. The National Parks represent about 8.4% of the country area. In this study, the collection sites are situated in Yangmingshan, Shei-Pa, Yushan, and Kenting National Park. Due to the island isolation, the proportions of endemic species are great in Taiwan, which also presents a high biodiversity. There are 4255 species of vascular plants including 1133 endemic. 5936 species in 1276 genera of fungi are hitherto reported in Taiwan. Among them, 233 Corticiaceae species were recorded, over one third (79 species) of them are known only from Taiwan. The first fungal report in Taiwan is about Phytophthora cyperi, published by the Japanese researcher T. Kawakami in 1904. Therefore, the history of research about fungi in Taiwan is more than one hundred years old. An eminent Japanese mycologist K. Sawada made an intensive survey from 1919 to 1959, and reported 2464 fungi species in his eleven volumes of “Descriptive Catalogue of Formosan Fungi”. However, only a few species (21 species in 9 genera) of Corticiaceae were recorded. From 1973, Chen and Lin resumed the study on Corticiaceae, and also some other foreign mycologists contributed for this field after 1980. The German research group lead by Franz Oberwinkler from Tübingen University collected in Taiwan several times. They published a number of new species and new records. Since 1989, S. H. Wu, a Taiwanese mycologist, has published a great amount of reports on corticioid fungi from Taiwan. Corticioid fungi were made up by the large and heterogeneous unnatural family Corticiaceae and other resupinate fungi belonging to other natural families in the Agaricomycetes. Molecular studies have shown that corticioid genera are distributed across all major clades of Agaricomycetes indicating that the corticioid fungi represent a polyphyletic group. They have resupinate fruitbodies and similar habitats. Species are characterized by simple fruitbody, more or less effused, and present smooth, porioid, grandinioid to odontioid hymenial surface. The fruitbodies are differently colored and usually soft to tough. Most of the Corticiaceae species are wood-saprobic organisms and gain the energy from the decomposing of wood-substrate such as cellulose or lignin. Materials for this study were collected by the author and other mycologists in Taiwan during surveys in April and May 1996, and March 2007, using the spring season with its high humidity and warm climate which are optimal conditions for the development of fungi. For assembling, the convenience sampling method was used in this study. This approach was chosen because it enables to detect a high biodiversity in a short time, and also to find species with rare or patchy distribution. The collecting sites from the North to the South include four National Parks and some preserved forests. They cover many different habitats such as low lands and high mountains. Fresh specimens were dried and analysed with a light microscope. 265 specimens belonging to Corticiaceae were studied in this research. Among them, 50 species in 21 genera including 11 new records and 10 new species were described with text and drawing. Four new species are belonging to Hyphodontia (H. sp. nov. 1, H. sp. nov. 2, H. sp. nov. 3, and H. sp. nov. 4), four to Schizopora (Sch. sp. nov. 1, Sch. sp. nov. 2, Sch. sp. nov. 3, and Sch. sp. nov. 4), one in Trechispora (T. sp. nov. 1), and one in Tubulicrinis (T. sp. nov. 1). Species recorded as new are Aleurodiscus amorphus, Botryohypochnus isabellinus, Hyphodontia cineracea, Hyphodontia palmae, Hypochnicium vellereum, Merulius tremellosus, Metulodontia nivea, Paullicorticium ansatum, Phlebia radiata, Phlebiella ardosiaca, and Xylobolus frustulatus. Besides, Botryohypochnus, Merulius, Metulodontia, Paullicorticium, and Xylobolus are also newly recorded genera in Taiwan. The genus Hyphodontia presents the highest diversity with 20 out of 50 species recorded. The second important genus is Hyphoderma, however with only 5 species. This indicates that Hyphodontia and Hyphoderma have a higher ability to develop in variable environments and approximately shows the predominance of these two genera in Taiwanese Corticiaceae. There are 11 new records out of the 50 species recorded, representing 22%. Some species, e.g. Hypochnicium vellereum and Paullicorticium ansatum were in the past recorded only in Europe and North America with cold and temperate climate. The samples of them are for the first time found in the subtropical belt, and display some difference from those of temperate regions. These collections should be molecularly investigated to clarify if they represent the same species of temperate areas. Patchily distributed species, for example Phlebiella ardosiaca, previously known only in Europe, and Hyphodontia palmae collected only in Brazil, were first recorded in different continents. Two possibilities are indicated by these new records: they are worldwide species but very rare to be found, or the Taiwanese specimens are taxonomically different. More survey from other continents and molecular study for these collections should be done in the future to solve this question. The distribution of Corticiaceae in Taiwan presents the variations in the north, central, and south areas and shows the diversity in lowlands and high mountains. The results of this study provide the evidence that the temperate Corticiaceae species displays a wider distribution. Subtropical and tropical taxa probably have also high dispersal capacities, and could possibly be found in the future in neighboring areas such as China, Japan, Korea or South Asia, but this needs further researches. In the total of 50 species, 10 new taxa were described in this study, giving about 20%. Some new species (e.g. Hyphodontia sp. 1, Hyphodontia sp. 2, and Hyphodontia sp. 3) are very similar to known species (Hyphodontia sambuci and Hyphodontia formosana), and the distinctive characters of Schizopora sp. nov. 1 are intermediate between those of Schizopora paradoxa and Hyphodontia flavipora. Thus, these small differences between the new and known species, suggest that the speciation occurred when the fungi migrated into Taiwan, due to the high diversity of environment, and amounts of the endemic plants. Taiwan is an intermediate place for the south (tropical) fungal species to migrate and adapt to north (temperate) regions. The middle and high altitude environments in Taiwan offer good conditions for the fungal speciation and possibly the occurrence of physiological changes to adapt to the temperate climate. Thus Taiwan has an important position for the biogeography of Asia mycobiota. 5936 known species in Taiwan represent about only 20% of the estimated number (24000) of Taiwanese fungal taxa. In this study, the findings (22% new records and 20% new species) indicate that amounts of unknown fungi species are expected in Taiwan. The lack of knowledge indicates that many new species are awaiting description, and fungal survey in Taiwan remains in a Pioneer phase. The last three wide surveys of Corticiaceae researches took place 20 years before this study (Chen & Lin 1977, Lin & Chen 1989, Wu 1990). After previous important contributions, the present taxonomic study comprising 21 genera is the most extensive on Corticiaceae of Taiwan.

Characterization of Novel Fabry Pérot Filter Arrays for Nanospectrometers in Medical Applications

Optische Spektroskopie ist eine sehr wichtige Messtechnik mit einem hohen Potential für zahlreiche Anwendungen in der Industrie und Wissenschaft. Kostengünstige und miniaturisierte Spektrometer z.B. werden besonders für moderne Sensorsysteme “smart personal environments” benötigt, die vor allem in der Energietechnik, Messtechnik, Sicherheitstechnik (safety and security), IT und Medizintechnik verwendet werden. Unter allen miniaturisierten Spektrometern ist eines der attraktivsten Miniaturisierungsverfahren das Fabry Pérot Filter. Bei diesem Verfahren kann die Kombination von einem Fabry Pérot (FP) Filterarray und einem Detektorarray als Mikrospektrometer funktionieren. Jeder Detektor entspricht einem einzelnen Filter, um ein sehr schmales Band von Wellenlängen, die durch das Filter durchgelassen werden, zu detektieren. Ein Array von FP-Filter wird eingesetzt, bei dem jeder Filter eine unterschiedliche spektrale Filterlinie auswählt. Die spektrale Position jedes Bandes der Wellenlänge wird durch die einzelnen Kavitätshöhe des Filters definiert. Die Arrays wurden mit Filtergrößen, die nur durch die Array-Dimension der einzelnen Detektoren begrenzt werden, entwickelt. Allerdings erfordern die bestehenden Fabry Pérot Filter-Mikrospektrometer komplizierte Fertigungsschritte für die Strukturierung der 3D-Filter-Kavitäten mit unterschiedlichen Höhen, die nicht kosteneffizient für eine industrielle Fertigung sind. Um die Kosten bei Aufrechterhaltung der herausragenden Vorteile der FP-Filter-Struktur zu reduzieren, wird eine neue Methode zur Herstellung der miniaturisierten FP-Filtern mittels NanoImprint Technologie entwickelt und präsentiert. In diesem Fall werden die mehreren Kavitäten-Herstellungsschritte durch einen einzigen Schritt ersetzt, die hohe vertikale Auflösung der 3D NanoImprint Technologie verwendet. Seit dem die NanoImprint Technologie verwendet wird, wird das auf FP Filters basierende miniaturisierte Spectrometer nanospectrometer genannt. Ein statischer Nano-Spektrometer besteht aus einem statischen FP-Filterarray auf einem Detektorarray (siehe Abb. 1). Jeder FP-Filter im Array besteht aus dem unteren Distributed Bragg Reflector (DBR), einer Resonanz-Kavität und einen oberen DBR. Der obere und untere DBR sind identisch und bestehen aus periodisch abwechselnden dünnen dielektrischen Schichten von Materialien mit hohem und niedrigem Brechungsindex. Die optischen Schichten jeder dielektrischen Dünnfilmschicht, die in dem DBR enthalten sind, entsprechen einen Viertel der Design-Wellenlänge. Jeder FP-Filter wird einer definierten Fläche des Detektorarrays zugeordnet. Dieser Bereich kann aus einzelnen Detektorelementen oder deren Gruppen enthalten. Daher werden die Seitenkanal-Geometrien der Kavität aufgebaut, die dem Detektor entsprechen. Die seitlichen und vertikalen Dimensionen der Kavität werden genau durch 3D NanoImprint Technologie aufgebaut. Die Kavitäten haben Unterschiede von wenigem Nanometer in der vertikalen Richtung. Die Präzision der Kavität in der vertikalen Richtung ist ein wichtiger Faktor, der die Genauigkeit der spektralen Position und Durchlässigkeit des Filters Transmissionslinie beeinflusst.

Optimierung der laserinduzierten Plasmaspektroskopie an Metallen durch Femtosekunden-Doppelpulse für die Entwicklung eines hochauflösenden 3D-Rasterabbildungsverfahrens

Die laserinduzierte Plasmaspektroskopie (LIPS) ist eine spektrochemische Elementanalyse zur Bestimmung der atomaren Zusammensetzung einer beliebigen Probe. Für die Analyse ist keine spezielle Probenpräparation nötig und kann unter atmosphärischen Bedingungen an Proben in jedem Aggregatzustand durchgeführt werden. Femtosekunden Laserpulse bieten die Vorteile einer präzisen Ablation mit geringem thermischen Schaden sowie einer hohen Reproduzierbarkeit. Damit ist fs-LIPS ein vielversprechendes Werkzeug für die Mikroanalyse technischer Proben, insbesondere zur Untersuchung ihres Ermüdungsverhaltens. Dabei ist interessant, wie sich die initiierten Mikrorisse innerhalb der materialspezifschen Struktur ausbreiten. In der vorliegenden Arbeit sollte daher ein schnelles und einfach zu handhabendes 3D-Rasterabbildungsverfahren zur Untersuchung der Rissausbreitung in TiAl, einer neuen Legierungsklasse, entwickelt werden. Dazu wurde fs-LIPS (30 fs, 785 nm) mit einem modifizierten Mikroskopaufbau (Objektiv: 50x/NA 0.5) kombiniert, welcher eine präzise, automatisierte Probenpositionierung ermöglicht. Spektrochemische Sensitivität und räumliches Auflösungsvermögen wurden in energieabhängigen Einzel- und Multipulsexperimenten untersucht. 10 Laserpulse pro Position mit einer Pulsenergie von je 100 nJ führten in TiAl zum bestmöglichen Kompromiss aus hohem S/N-Verhältnis von 10:1 und kleinen Lochstrukturen mit inneren Durchmessern von 1.4 µm. Die für das Verfahren entscheidende laterale Auflösung, dem minimalen Lochabstand bei konstantem LIPS-Signal, beträgt mit den obigen Parametern 2 µm und ist die bislang höchste bekannte Auflösung einer auf fs-LIPS basierenden Mikro-/Mapping-Analyse im Fernfeld. Fs-LIPS Scans von Teststrukturen sowie Mikrorissen in TiAl demonstrieren eine spektrochemische Sensitivität von 3 %. Scans in Tiefenrichtung erzielen mit denselben Parametern eine axiale Auflösung von 1 µm. Um die spektrochemische Sensitivität von fs-LIPS zu erhöhen und ein besseres Verständnis für die physikalischen Prozesse während der Laserablation zu erhalten, wurde in Pump-Probe-Experimenten untersucht, in wieweit fs-Doppelpulse den laserinduzierten Abtrag sowie die Plasmaemission beeinflussen. Dazu wurden in einem Mach-Zehnder-Interferometer Pulsabstände von 100 fs bis 2 ns realisiert, Gesamtenergie und Intensitätsverhältnis beider Pulse variiert sowie der Einfluss der Materialparameter untersucht. Sowohl das LIPS-Signal als auch die Lochstrukturen zeigen eine Abhängigkeit von der Verzögerungszeit. Diese wurden in vier verschiedene Regimes eingeteilt und den physikalischen Prozessen während der Laserablation zugeordnet: Die Thermalisierung des Elektronensystems für Pulsabstände unter 1 ps, Schmelzprozesse zwischen 1 und 10 ps, der Beginn des Abtrags nach mehreren 10 ps und die Expansion der Plasmawolke nach über 100 ps. Dabei wird das LIPS-Signal effizient verstärkt und bei 800 ps maximal. Die Lochdurchmesser ändern sich als Funktion des Pulsabstands wenig im Vergleich zur Tiefe. Die gesamte Abtragsrate variiert um maximal 50 %, während sich das LIPS-Signal vervielfacht: Für Ti und TiAl typischerweise um das Dreifache, für Al um das 10-fache. Die gemessenen Transienten zeigen eine hohe Reproduzierbarkeit, jedoch kaum eine Energie- bzw. materialspezifische Abhängigkeit. Mit diesen Ergebnissen wurde eine gezielte Optimierung der DP-LIPS-Parameter an Al durchgeführt: Bei einem Pulsabstand von 800 ps und einer Gesamtenergie von 65 nJ (vierfach über der Ablationsschwelle) wurde eine 40-fache Signalerhöhung bei geringerem Rauschen erzielt. Die Lochdurchmesser vergrößerten sich dabei um 44 % auf (650±150) nm, die Lochtiefe um das Doppelte auf (100±15) nm. Damit war es möglich, die spektrochemische Sensitivität von fs-LIPS zu erhöhen und gleichzeitig die hohe räumliche Auflösung aufrecht zu erhalten.

Growth and Characterization of LiCoO₂ Thin Films for Microbatteries

LiCoO₂thin films have been grown by pulsed laser deposition on stainless steel and SiO₂/Si substrates. The film deposited at 600°C in an oxygen partial pressure of 100mTorr shows an excellent crystallinity, stoichiometry and no impurity phase present. Microstructure and surface morphology of thin films were examined using a scanning electron microscope. The electrochemical properties of the thin films were studied with cyclic voltammetry and galvanostatic charge-discharge techniques in the potential range 3.0-4.2 V. The initial discharge capacity of the LiCoO2 thin films deposited on the stainless steel and SiO₂/Si substrates reached 23 and 27 µAh/cm², respectively.

Grain size analyses in tin-lead glazes based on 2d-sections

A problem in the archaeometric classification of Catalan Renaissance pottery is the fact, that the clay supply of the pottery workshops was centrally organized by guilds, and therefore usually all potters of a single production centre produced chemically similar ceramics. However, analysing the glazes of the ware usually a large number of inclusions in the glaze is found, which reveal technological differences between single workshops. These inclusions have been used by the potters in order to opacify the transparent glaze and to achieve a white background for further decoration. In order to distinguish different technological preparation procedures of the single workshops, at a Scanning Electron Microscope the chemical composition of those inclusions as well as their size in the two-dimensional cut is recorded. Based on the latter, a frequency distribution of the apparent diameters is estimated for each sample and type of inclusion. Following an approach by S.D. Wicksell (1925), it is principally possible to transform the distributions of the apparent 2D-diameters back to those of the true three-dimensional bodies. The applicability of this approach and its practical problems are examined using different ways of kernel density estimation and Monte-Carlo tests of the methodology. Finally, it is tested in how far the obtained frequency distributions can be used to classify the pottery

A practical approach on boar sperm cryodamage. Morphofunctional and immunocytochemical study of cryopreserved boar sperm intended for use in artificial insemination

L'ús d'esperma criopreservada en la inseminació artificial (IA) d'espècies d'interès productiu permet un major control sanitari i la creació de bancs de germoplasma d'alt valor genètic, entre d'altres avantatges. En el mercat porcí la major part de les inseminacions són encara realitzades amb semen refrigerat degut a l'èxit de l'aplicació de diluents de llarga durada i també a causa de la sensibilitat de l'esperma porcina a la criopreservació. Malgrat que aquesta sensibilitat ve donada per característiques particulars de la fisiologia espermàtica en l'espècie, algunes ejaculacions mantenen els paràmetres de qualitat espermàtica després de la criopreservació (ejaculacions amb bona "congelabilitat", GFEs) enfront d'altres que no sobreviuen al procés (ejaculacions amb mala "congelabilitat", PFEs). El primer objectiu de l'estudi va ser comparar ambdós grups en termes de fertilitat in vivo. El segon objectiu va ser testar l'eficiència de la inseminació postcervical (post-CAI) amb l'esperma criopreservada. El tercer objectiu va ser buscar predictors de la congelabilitat de les ejaculacions, tant en les GFEs com en les PFEs i en tres passos del procés de criopreservació (a 17ºC, a 5ºC i a 240 min postdescongelació). Aquest objectiu es va dur a terme mitjançant l'avaluació de paràmetres convencionals de qualitat espermàtica i a través de l'estudi de la localització i la reactivitat sota el microscopi de tres proteïnes (GLUT3, HSP90AA1 i Cu/ZnSOD) relacionades amb la fisiologia espermàtica i amb possibles rols en la congelabilitat. El quart objectiu va ser quantificar l'expressió de les tres proteïnes per transferència western, tant en espermatozoides d'ejaculacions GFEs com en els d'ejaculacions PFEs i en els tres passos abans esmentats, per tal de determinar el seu potencial com a predictores de la congelabilitat. Pel primer i el segon objectiu, 86 truges van ser inseminades per post-CAI amb 26 ejaculacions de mascles Piétrain dividides en una porció refrigerada a 17ºC (tractament control) i una porció criopreservada, ambdues porcions classificades alhora com a GFEs o PFEs. Els resultats més rellevants van demostrar que les probabilitats d'embaràs eren dues vegades menors en inseminacions amb esperma criopreservada d'ejaculacions PFEs (P < 0.05) que en inseminacions amb esperma criopreservada d'ejaculacions GFEs, fet que indica que les ejaculacions amb percentatges elevats d'espermatozoides mòbils progressius i d'integritat de membrana (per sobre del 40% en les GFEs) són més favorables a provocar embarassos que no pas aquelles ejaculacions amb una pobra funció espermàtica in vitro (PFEs). Ni el nombre de truges que van donar a llum, ni la quantitat de garrins, ni el risc de reflux espermàtic van ser significativament diferents entre les inseminacions amb esperma criopreservada d'ejaculacions GFEs i les inseminacions control amb semen refrigerat, la qual cosa demostra la bona aplicabilitat de la inseminació post-CAI amb l'esperma criopreservada. Finalment, pel tercer i quart objectius van ser criopreservades 29 i 11 ejaculacions de mascles Piétrain, respectivament. Dos paràmetres cinètics espermàtics, la linealitat (LIN) i la rectitud (STR), van mostrar una hiperactivació de la mobilitat superior en les ejaculacions PFEs que en les GFEs després de 30 min a 5ºC durant la criopreservació. A més, la combinació d'ambdós paràmetres va donar una fiabilitat propera al 72% en la predicció de la congelabilitat de les ejaculacions porcines. Tot i que no va ser possible predir la congelabilitat mitjançant l'avaluació de les tres proteïnes al microscopi, els resultats de transferència western van revelar diferències en l'expressió de la HSP90AA1 en l'esperma a 17ºC, molt possiblement relacionades amb la millor supervivència a la criopreservació dels espermatozoides d'ejaculacions GFEs. Aquests resultats suggereixen que la promoció de la criopreservació d'esperma porcina per la seva aplicació en IA passa pel desenvolupament de tests per la predicció de la congelabilitat en semen refrigerat.

Producció i caracterització de variants de la ribonucleasa pancreàtica humana dissenyades per a adquirir propietats citotòxiques

Amb la finalitat d'aprofundir en les bases moleculars de la citotoxicitat de les ribonucleases pancreàtiques, es van construir variants derivades de l'HP-RNasa seguint dues estratègies. En la primera, es van generar variants de l'enzim resistents a l'acció de l'inhibidor proteic de les ribonucleases (hRI), substituint residus implicats en la interfície de contacte entre la ribonucleasa i l'hRI. En la segona, es va addicionar el motiu RGD en regions de superfície de la proteïna implicades en la formació del complex amb l'hRI, a fi de promoure la seva interacció amb la membrana plasmàtica de les cèl·lules i a la vegada disminuir l'afinitat de les variants per l'hRI. Es va comprovar que només les variants portadores de substitucions múltiples adquirien la capacitat de resistència a l'hRI. L'estudi del percentatge d'inhibició de la síntesi proteica en cèl·lules incubades amb cadascuna de les variants va mostrar que només dues de les variants construïdes havien adquirit propietats citotòxiques. La citotoxicitat més elevada la va presentar una variant que no era resistent a l'hRI, amb valors que eren només entre 5 i 15 vegades inferiors als de l'onconasa. Aquest resultat demostrà que la sensibilitat a l'hRI no és necessàriament un paràmetre limitant per a la citotoxicitat de les ribonucleases. Cap de les variants que incorporava un motiu RGD presentà citotoxicitat, evidenciant que aquest motiu no és efectiu a fi de dotar les ribonucleases pancreàtiques de propietats citotòxiques. Es van estudiar les bases moleculars de la citotoxicitat de la variant més citotòxica. En primer lloc, l'anàlisi de la internalització per marcatge radioactiu d'aquesta variant en relació amb l'onconasa i amb altres variants de l'HP-RNasa no citotòxiques, va posar en evidència que només l'onconasa era internalitzada eficientment. Es descartava així la possibilitat que l'acció citotòxica de l'enzim estudiat fos conseqüència d'una major eficiència d'endocitosi. També es va comprovar que l'addició del motiu RGD no era capaç de promoure la internalització de les proteïnes amb més eficàcia. Per microscòpia confocal de fluorescència, les variants humanes només es van començar a detectar a l'interior de la cèl·lula a partir de les 24 h d'incubació. Totes les variants generades van presentar una eficiència catalítica superior al 50 % de l'activitat de la seva proteïna parental, PM5, indicant que probablement l'estructura del centre actiu no havia estat afectada de manera dràstica per les substitucions introduïdes. No obstant, en tots els casos es va produir una disminució en la termoestabilitat respecte a PM5. Aquest resultat indicà que la correlació descrita a la bibliografia entre l'increment de termoestabilitat i l'increment de citotoxicitat per les ribonucleases no sempre es compleix. Per microscòpia confocal es va comprovar que tant la proteïna més citotòxica, com una variant no citotòxica resistent a l'hRI, així com la proteïna parental, seguien la via de degradació lisosomal. Aquesta ruta de trànsit no va ser afectada per l'addició de drogues que alteren les vies de trànsit retrògrad (monensina i brefeldina A), però sí per l'addició de la bafilomicina A1, una droga que neutralitza el pH endosomal i que va actuar alentint el trànsit de les proteïnes als lisosomes. D'acord amb aquests resultats, els valors de citotoxicitat de les variants es van incrementar de manera significativa només en presència de bafilomicina A1, suggerint que les ribonucleases transloquen al citoplasma a partir d'algun punt de la via de trànsit endosomal. Es va comprovar que l'acció de la variant més citotòxica era deguda a que l'addició d'un segon motiu de tres Arg en PE5 dota a aquesta proteïna amb un senyal de transport nuclear. La fracció d'enzim que aconsegueix translocar al citoplasma a partir d'algun punt de la via endosomal previ als lisosomes, és conduït ràpidament al nucli de la cèl·lula per mitjà del mecanisme clàssic de transport actiu. Per la seva afinitat amb l'rRNA, l'enzim es concentra en el nuclèol, on probablement duu a terme la seva activitat catalítica. La interacció d'aquesta variant amb els receptors nucleocitoplasmàtics, les importines, impediria per altra banda el bloqueig de l'enzim per part de l'hRI. Els resultats obtinguts presenten una nova estratègia de disseny de ribonucleases citotòxiques, basada en l'addició de segments NLS a fi de promoure el transport nuclear dels enzims. Aquesta estratègia podria permetre superar limitacions que fins al moment han estat descrites com a limitants de la citotoxicitat de les ribonucleases pancreàtiques, com la sensibilitat a l'hRI o la baixa eficiència d'internalització.

Velocities of compressional and shear waves in limestones

Carbonate rocks are important hydrocarbon reservoir rocks with complex textures and petrophysical properties (porosity and permeability) mainly resulting from various diagenetic processes (compaction, dissolution, precipitation, cementation, etc.). These complexities make prediction of reservoir characteristics (e.g. porosity and permeability) from their seismic properties very difficult. To explore the relationship between the seismic, petrophysical and geological properties, ultrasonic compressional- and shear-wave velocity measurements were made under a simulated in situ condition of pressure (50 MPa hydrostatic effective pressure) at frequencies of approximately 0.85 MHz and 0.7 MHz, respectively, using a pulse-echo method. The measurements were made both in vacuum-dry and fully saturated conditions in oolitic limestones of the Great Oolite Formation of southern England. Some of the rocks were fully saturated with oil. The acoustic measurements were supplemented by porosity and permeability measurements, petrological and pore geometry studies of resin-impregnated polished thin sections, X-ray diffraction analyses and scanning electron microscope studies to investigate submicroscopic textures and micropores. It is shown that the compressional- and shear-wave velocities (V-p and V-s, respectively) decrease with increasing porosity and that V-p decreases approximately twice as fast as V-s. The systematic differences in pore structures (e.g. the aspect ratio) of the limestones produce large residuals in the velocity versus porosity relationship. It is demonstrated that the velocity versus porosity relationship can be improved by removing the pore-structure-dependent variations from the residuals. The introduction of water into the pore space decreases the shear moduli of the rocks by about 2 GPa, suggesting that there exists a fluid/matrix interaction at grain contacts, which reduces the rigidity. The predicted Biot-Gassmann velocity values are greater than the measured velocity values due to the rock-fluid interaction. This is not accounted for in the Biot-Gassmann velocity models and velocity dispersion due to a local flow mechanism. The velocities predicted by the Raymer and time-average relationships overestimated the measured velocities even more than the Biot model.

Problems with determining the particle size distribution of chalk soil and some of their implications

Particle size distribution (psd) is one of the most important features of the soil because it affects many of its other properties, and it determines how soil should be managed. To understand the properties of chalk soil, psd analyses should be based on the original material (including carbonates), and not just the acid-resistant fraction. Laser-based methods rather than traditional sedimentation methods are being used increasingly to determine particle size to reduce the cost of analysis. We give an overview of both approaches and the problems associated with them for analyzing the psd of chalk soil. In particular, we show that it is not appropriate to use the widely adopted 8 pm boundary between the clay and silt size fractions for samples determined by laser to estimate proportions of these size fractions that are equivalent to those based on sedimentation. We present data from field and national-scale surveys of soil derived from chalk in England. Results from both types of survey showed that laser methods tend to over-estimate the clay-size fraction compared to sedimentation for the 8 mu m clay/silt boundary, and we suggest reasons for this. For soil derived from chalk, either the sedimentation methods need to be modified or it would be more appropriate to use a 4 pm threshold as an interim solution for laser methods. Correlations between the proportions of sand- and clay-sized fractions, and other properties such as organic matter and volumetric water content, were the opposite of what one would expect for soil dominated by silicate minerals. For water content, this appeared to be due to the predominance of porous, chalk fragments in the sand-sized fraction rather than quartz grains, and the abundance of fine (<2 mu m) calcite crystals rather than phyllosilicates in the clay-sized fraction. This was confirmed by scanning electron microscope (SEM) analyses. "Of all the rocks with which 1 am acquainted, there is none whose formation seems to tax the ingenuity of theorists so severely, as the chalk, in whatever respect we may think fit to consider it". Thomas Allan, FRS Edinburgh 1823, Transactions of the Royal Society of Edinburgh. (C) 2009 Natural Environment Research Council (NERC) Published by Elsevier B.V. All rights reserved.