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Eingeladener Vortrag
- nein (26)
The system Na2O.B2O3-SiO2 (NBS) is the basis of many industrial glass applications and therefore one of the most studied systems at all. Glass formation is possible over a wide compositional range, but the system also contains ranges of pronounced phase separation and crystallization tendency. Despite its importance, experimental data are limited to few compositional areas. The general understanding and modelling of glass formation, phase separation, and crystallization in this system would therefore be easier if small step melt series could be studied. The efficient melting of such glass series is now possible with the new robotic glass melting system at the Federal Institute for Materials Research and Testing (BAM, Division Glasses). Using three exemplary joins within this NBS system, the small step changes of glass transition temperature (Tg), crystallization behavior as well as glass density (Roh) was studied. Additionally, experimental Tg and Roh data were compared with their modeled counterparts using SciGlass and a newly developed DFT model, respectively.
Alternativer Holzschutz
(2004)
Aluminas resulting from sols prepared via a modified Yoldas procedure were studied with differential thermal analysis (DTA), differential thermal gravimetrie (DTG), 27Al nuclear magnetic resonance (27Al MAS NMR) and X-ray diffraction (XRD) concerning their thermal properties, aluminum speciation and phase content.
Hydrolysis of aluminum-sec-butoxide in aluminum nitrate solutions allowed to prepare stable sols with varying NO3-/Al molar ratios, solids contents and pH values. Resulting sols contained different aluminum species including also Al13 polycations. Sol preparation conditions also determined aluminum speciation in solid products obtained after thermal treatments of gels obtained from these sols. Al13 polycations and AlO5 species were found to play an important role for thermally induced transformation from amorphous products via eta-Al2O3 to alpha-Al2O3. Intermediately formed eta-Al2O3 promotes the phase transformation to alpha-Al2O3.
Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography
(SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands.
To explore the impact of ambient and structural water on static fatigue, the initiation and growth of 3279 Vickers induced median radial cracks were automatically recorded and analyzed. We find that humidity is more efficient in initiating cracks and promoting their growth than water, which is dissolved in the glass structure. In particular for slow crack growth (< 3x10-6 m s-1), tests in dry nitrogen showed a considerable decrease in the crack growth exponent with increasing water content of the glasses. On the other hand, if tests were performed in humid air, the crack growth exponent was independent of the water content of the hydrous glasses, while stress intensity decreased slightly. These observations indicate that water promotes the processes at the crack-tip regardless of its origin. However, ambient water is more efficient.
Open cell rigid foams made from polyurethane (PU) are frequently used in ceramic processing for preparation of porous ceramics by the so-called replica technique. This work presents data regarding the PU burnout, shrinkage characteristics as well as the morphology of the ceramic coated PU sponges during heating up. Shrinkage of the ceramic coated PU sponges closely follows the mass loss due to PU decomposition. Two temperatures (i) 267 °C and (ii) 380 °C were identified at which PU decomposition reaches local maxima. Shrinkage measurements on ceramic coated PU sponges reveal that both PU decomposition stages lead to similar extends of shrinkage in the ceramic coated PU sponge. Differential thermal analysis (DTA) showed that the two decomposition related temperatures (267 and 380 °C) differ concerning the energy release. While the low-temperature signal is endothermic, an exothermic signal was detected at 380 °C. The morphology of the ceramic coated PU sponges was investigated with scanning electron microscopy (SEM) which gave insight into the formation of hollow ceramic struts-a well known feature of ceramics being prepared by the replica technique.
New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials.
It has been shown that tetraethoxysilane-derived precursors are suitable solutions for impregnating pine sapwood to improve its dimensional stability. Tailored sol–gel syntheses result in precursors with nano-scaled silica species which are able to penetrate into the cell walls of wood. The physical fixation of those species inside the cell walls was verified by ESEM/EDX investigations. There is evidence that the silica species are chemically bonded to wood components. Nonreacted alkoxy groups can exist in the wood composites after impregnation. The amount of these organic residues depends on the composition of the precursors, especially their condensation degree and reactivity. Treatments for finishing the composites after the impregnation step to get clean products and stable properties are discussed in this context. An explanation of the complex relationship between solids content in the impregnation solutions and percentage weight gain and bulking of the composites is given. It can be demonstrated that high WPG values (>20 %) are pre-conditions for an effective protection of the resulting composites but they only guarantee efficient improvements if connected with the incorporation of the inorganic component inside the cell walls. Therefore, the sol–gel syntheses have to be carried out in such a manner that very small (<2 nm) as well as reactive species are sufficiently available. This demands syntheses using sub-stoichiometric water contents (H2O/TEOS <4, better <2).
Stable crack growth was measured for nominal dry and water-bearing (6 wt%) soda-lime silicate glasses in double cantilever beam geometry and combined with DMA studies on the effects of dissolved water on internal friction and glass transition, respectively. In vacuum, a decreased slope of logarithmic crack growth velocity versus stress intensity factor is evident for the hydrous glass in line with an increase of b-relaxation intensity indicating more energy Dissipation during fracture. Further, inert crack growth in hydrous glass is found to be divided into sections of different slope, which indicates different water related crack propagation mechanism. In ambient air, a largely extended region II is observed for the hydrous glass, which indicates that crack growth is more sensitive to ambient water.
We measured and collected literature data for the crystal growth rate, u(T), of µ-cordierite (2MgO · 2Al2O3 · 5SiO2) and diopside (CaO · MgO · 2SiO2) in their isochemical glass forming melts. The data cover exceptionally wide temperature ranges, i.e. 8001350 °C for cordierite and 7501378 °C for diopside. The maximum of u(T) occurs at about 1250 °C for both systems. A smooth shoulder is observed around 970 °C for µ-cordierite. Based on measured and collected viscosity data, we fitted u(T) using standard crystal growth models. For diopside, the experimental u(T) fits well to the 2D surface nucleation model and also to the screw dislocation growth mechanism. However, the screw dislocation model yields parameters of more significant physical meaning. For cordierite, these two models also describe the experimental growth rates. However, the best fittings of u(T) including the observed shoulder, were attained for a combined mechanism, assuming that the melt/crystal interface growing from screw dislocations is additionally roughened by superimposed 2D surface nucleation at large undercoolings, starting at a temperature around the shoulder. The good fittings indicate that viscosity can be used to assess the transport mechanism that determines crystal growth in these two systems, from the melting point Tm down to about Tg, with no sign of a breakdown of the StokesEinstein/Eyring equation.
Crystallization behavior in different atmospheres (air, Ar, and 7% H2/Ar) of lithium iron phosphate glass (33Li2O33Fe2O31Nb2O5–33P2O5 (LFNP)) powders with different sizes of 2–1000 µm was examined. The crystallization peak temperature (Tp) in Ar and 7% H2/Ar decreased with decreasing the particle size of glass powders, but the value of Tp in air was independent of particle size. The crystallized glass obtained by heating to Tp showed the formation of the α-Li3Fe2(PO4)3 and LiFePO4 crystalline phases. Fe2O3 crystals were formed only in the inside of crystallized glass plates in the heating in air. The crystallization of LiFePO4 was largely enhanced in the particle size of <2 µm during the heating in Ar and 7% H2/Ar atmospheres. The main crystallization mechanism in LFNP glass was found to be surface crystallization. Significant shrinkages were observed for glass compacts (pellets) in the heating in 7% H2/Ar. These results suggest that controlling particle sizes and atmospheres enables the design the morphology of LiFePO4 crystals in LFNP glass.
The effect of structural water on density, elastic constants and microhardness of water-bearing soda-lime-silica glasses of up to 21.5 mol% total water is studied. It is found that the Poisson ratio and the water content are positively correlated, while density and the elastic moduli decrease with increasing water content. Vickers hardness decreases by approximately 27% from the dry to the most hydrous glass. For water fractions <3 mol%, the dependencies are non-linear reflecting the non-linear change in the concentrations of OH and H2O molecules dissolved, whereas for water fractions >3 mol% linear dependencies are found. To distinguish the effect of structural water and environmental water, indentations were performed in toluene, nitrogen gas and air. Timedependent softening was evident for testing dry glasses in humid atmospheres as well as for tests of hydrous glasses in dry atmospheres. This indicates that the response times of dissolved water species are effectively equal in both scenarios.
Development of wood-inorganic composites with enhanced properties and environmental stability
(2002)
Development of wood-inorganic composites with enhanced properties and environmental stability
(2002)
This work compares thin layers (films) and monoliths prepared from alumina sols with respect to their microstructure, thermal evolution, porosity and specific surface area. After heat treatment at similar temperatures, films and monoliths showed the same qualitative changes in porosity and specific surface area. However, some marked quantitative differences were detected. Film fragments had a lower open porosity, a lower specific surface area and a narrower pore size distribution. Furthermore, the thermal evolution showed a markedly different burnout of organic components between films and monoliths. The observed differences between films and monolith can be explained by the ageing history of the sols during sample preparation.
The sintering of Low Temperature Co-fired Ceramics prepared from alumoborosilicate
glass- and Al2O3 powders of similar small particle size was studied by dilatometry, heating microscopy,
microstructure analysis, glass- and effective viscosity measurements. The steric effect of
Al3O3 inclusions was studied using a gnon-reactiveh model composite. With increasing Al3O3 volume
fraction (Φ ≤ 0.45), sintering decelerates and its final stage shifts to higher temperature. The
attainable shrinkage is reduced as Al2O3 particle clusters bearing residual pores become more frequent.
The kinetics of sintering could be described formally superposing the weighed contributions
of differentially sized and randomly composed glass-crystal particle clusters and assuming a sintering
rate controlled by the effective matrix viscosity, which increases with Φ and with progressive
wetting of Al2O3 particles during densification. The "reactive" model composite shows significant
dissolution of Al2O3 into the glass, which has two opposed effects on sintering: reducing Φ and increasing
glass viscosity. For the present case (Φ = 0.25), the latter effect dominates and sintering is
retarded by Al2O3 dissolution. Crystallization of wollastonite starts after full densification. Dissolution
of Al2O3 was found to promote the subsequent growth of anorthite.
Barium silicate glass powders 4 h milled in CO2 and Ar and sintered in air are studied with microscopy, total carbon analysis, differential thermal Analysis (DTA), vacuum hot extraction mass spectroscopy (VHE-MS), Fourier-transformed infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary-ion mass spectrometry (TOF-SIMS). Intensive foaming of powder compacts is evident, and VHE studies prove that foaming is predominantly caused by carbonaceous species for both milling gases. DTA Shows that the decomposition of BaCO3 particles mix-milled with glass powders occurs at similar temperatures as foaming of compacts. However, no carbonate at the glass surface could be detected by FTIR spectroscopy, XPS, and TOF-SIMS after heating to the temperature of sintering. Instead, CO2 molecules unable to rotate identified by FTIR spectroscopy after milling, probably trapped by mechanical dissolution into the glass bulk. Such a mechanism or microencapsulation in cracks and particle aggregates can explain the contribution of Ar to foaming after intense milling in Ar atmosphere. The amount of CO2 molecules and Ar, however, cannot fully explain the extent of foaming. Carbonates mechanically dissolved beneath the surface or encapsulated in cracks and micropores of particle aggregates are therefore probably the major foaming source.
Glass
(2019)
Overview about the key activities of division 5.6 glass and the diversity of the material glass. For the vacuum hot extraction method (VHE-MS) some examples are presented e. g. for the measurement of water content or the determination of diffusion coefficient of hydrogen in glasses. Finally, an outlook is shown on the robot controlled glass screening device which will be available next year.
Boron oxide glasses usually show low glass transition temperature Tg due to the three-fold oxygen coordination of boron. Adding of alkali and alkaline earth oxides to the glass composition will not decrease but increase Tg due to a change in boron coordination from trigonal to tetrahedral, known as the boron anomaly. Only for higher fractions of alkali oxides, non-bridging oxygens (NBO) are progressively formed in competition with tetrahedrally coordinated boron, which leads to a decrease in viscosity.
ln contrast to this well-known behavior of alkali oxides (R2O), there is little known about adding H2O to borate glasses. The present work therefore aims in shedding light on the rheological properties of hydrous soda lime borate glasses with particular focus on the role of water. For doing so, we determined Tg as a function of Na2O and H2O content using differential thermal analysis (DTA) backed up by micropenetration viscosity measurements. Results show that water decreases Tg for all glasses and water concentrations under study (< 8 wt.% total water). Obviously, water mostly causes the formation of NBO having no significant influence on boron coordination as seen for alkaline.
Die offenporige Struktur des Holzes und dessen chemische Zusammensetzung bieten sich an, über Tränkverfahren geeignete Precursoren so an den inneren Oberflächen des Holzes zu fixieren, dass bei anschließender thermischer Behandlung ein umweltfreundlicher anorganisch-organischer Verbundwerkstoff entsteht. Aus der Literatur sind hierzu verschiedene Ansätze bekannt. - Ziel der vorliegenden Arbeit sind Verbesserungen der biologischen Beständigkeit, der Feuchtebeständigkeit unter Beibehaltung bzw. leichter Verbesserung der mechanischen Eigenschaften des Holzes. Dies wird durch eine chemische Verbindung (Haftung) zwischen den verbundbildenden Phasen Holz und Precursor und eventuell zusätzlichen Einbau von funktionellen organischen Gruppen realisiert. Als Precursoren dienen über den Sol-Gel Weg hergestellte Kieselsole, die nach vollständiger thermischer Umsetzung zu rein anorganischen Phasen (SiO2) führen. Die Sol-Gel Synthese konnte so optimiert werden, dass durch die Behandlung eine homogene Beschichtung aller Oberflächen erreicht werden kann.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
The permeation of hydrogen gas was studied in meta-aluminous (tectosilicate) glass powders of Li2O×Al2O3×SiO2 (LAS), Na2O×Al2O3×SiO2 (NAS) and MgO×Al2O3×SiO2 (MAS) systems by pressure loading and vacuum extraction in the temperatures range 210–310 °C. With this method, both the solubility S and the diffusivity D were determined, while the permeability was given by the product SD. For all glasses, S was found to decrease with temperature, while D increased. Since the activation energy of diffusion of H2 molecules exceeded that of dissolution, permeation increased slightly with temperature. When extrapolated to standard conditions (25 °C), the permeability of tectosilicate glasses was found to be only 10-22–10-24 mol H2 (m s Pa)-1, which is 8–10 magnitudes lower than most polymers. Thin glass liners of these compositions are expected to be the most effective barrier for tanks of pressurised hydrogen.
Physical storage of gaseous hydrogen under high-pressure in glassy micro-containers such as spheres and capillaries is a promising concept for enhancing safety and the volumetric capacity of mobile hydrogen storage systems. As very low permeation through the container wall is required for storage of compressed hydrogen, development of glasses of minimal hydrogen permeability is needed. For this purpose, one has to understand better the dependence of hydrogen permeability on glass structure. The paper points out that minimizing the accessible free volume is as one strategy to minimize hydrogen permeability. Based on previously measured and comprehensive literature data, it is shown that permeation is independently controlled by ionic porosity and network modifier content. Thus, ionic porosity in modified and fully polymerized networks can be decreased equally to the lowest hydrogen permeability among the glasses under study. Applying this concept, a drop of up to 30,000 with respect to the permeation of hydrogen molecules through silica glass is attainable.
Increasing Exposed Metal Site Accessibility in a Co-MOF-74 Material With Induced Structure-Defects
(2019)
Metal-organic frameworks (MOFs) are promising nanoporous materials with many practical applications. This owes largely to their remarkable porosity and the presence of specific chemical functionalities, such as exposed metal sites (EMS). The MOF-74 structure is known for exhibiting one of the highest EMS densities among porous materials. Moreover, the inclusion of structural defects has been proposed to enhance activity further. This was previously achieved by mixing the original linker together with a second one, having lower topology. The presence of structural defects was evidenced by the resulting crystalline properties and thermal stability. In this work, different mixtures of tetratopic 2,5-dihydroxyterephthalic acid with up to 60% of the tritopic hydroxyterephtalic acid were used to synthesize crystalline Co-MOF-74-like materials. Materials synthesized from higher proportions than 30% of hydroxyterephtalic acid in the synthesis media collapse upon partial removal of the solvent molecules. This indicates the presence of structural defects and the importance of the solvent molecules in stabilizing the crystalline structures. Electron microscope images show that crystal size reduces with inclusion of hydroxyterephtalic acid as the second linker. The presence of coordinated solvent molecules at the EMS was evaluated by Fourier-transform infrared spectra (FTIR) spectroscopy, so that a higher degree of solvent-exchange was observed during washing for defective structures. Furthermore, TG analysis suggests defective structures exhibit lower desolvation temperatures than the defect-free structures. Finally, N2 adsorption-desorption analyses at −196°C showed an enhanced accessibility of the gas to the inner porosity of the defective structures and therefore, the EMS of the material. All these finding make this pathway interesting to enhance the potential interest of these materials for an industrial application because of both a facilitated activation and a better access to the active sites.
Iron aluminides, already reported in the late 19th century, did not cease to attract the interest of scientists and engineers ever since. Besides good oxidation resistance, low density and resource availability, potentials for hightemperature strengths that compete with high-alloy steels were unlocked by low alloy contents. Still, research on alloy design continues, as alloying usually comes at the price of brittleness in low-temperature regimes. A potential candidate is the quinary Fe–Al–Mo–Ti–B system which is strengthened by solid solution and eutectic borides. It was shown to have good strength and outstanding creep resistance under compressive loading up to elevated temperatures. Although the individual effect of alloy additions is well understood in iron aluminides, little is known about the combined effects of alloying concentrations on microstructure, phase stability and mechanical properties. Therefore a systematic study of two Ti-doped near-Fe3Al alloys with varying contents of Mo (2–4 at.%) and B (0.5–1 at.%) was conducted. In total eight different alloys were fabricated by investment casting into ceramic shell molds. Alloys were characterized and compared by grain size, phase transitions, microstructure evolution as well as elemental compositions and volume fractions of phases. For mechanical characterization, macrohardness and microhardness tests as well as tensile tests at ambient and high tempera tures were conducted. Independent of alloy additions, alloys with 24–25 at.% Al exhibit superior proof strength due to a higher matrix hardness. Decreasing B content generally decreases strength by lower secondary phase fractions which contribute via particle hardening. Reducing Mo content decreases both the solute concentration in the matrix and secondary phase fractions. Surprisingly, strength is similar or even superior to alloys with higher Mo content. Strength relations are discussed with a focus on solid-solution hardening theory and other competing strengthening mechanisms.
The internal friction of hydrated soda-lime-silica glasses with total water content (CW ) up to 1.9 wt. % was studied by dynamic mechanical analysis (DMA) using temperature-frequency sweeps from 723 K to 273 K and from 1 s-1 to 50 s-1. Total water content and concentrations of H2O molecules (CH2O ) and OH groups (COH) in the DMA specimens were determined by infrared spectroscopy. For low water contents (CW ≈ COH < 0.25 wt. %) two discrete internal friction peaks below the glass transition (α relaxation) were assigned to the low-temperature motion of alkali ions (γ relaxation) and cooperative movements of dissimilar mobile species under participation of OH at higher temperature (βOH relaxation). For large water contents (CW > 1 wt. %), where significant amounts of molecular water are evident (CH2O > 0.15 wt. %), however, internal friction spectra change unexpectedly: the βOH peak heights saturate and a low temperature shoulder appears on the β-relaxation peak. This emerging relaxation mode (βH2O relaxation) was assigned to the motions of H2O molecules. βH2O relaxation was found to be faster than βOH but slower than γ relaxation. Activation energy of the different relaxation modes increased in the order γ < βH2O < βOH < α.
We present an easy-to-apply method to predict structural trends in the internal nucleation tendency of oxide glasses. The approach is based on calculated crystal fracture surface energies derived from easily accessible diatomic bond energy and crystal lattice data. The applicability of the method is demonstrated on literature nucleation data for isochemically crystallizing oxide glasses.